JP6836646B2 - Polyfunctional monomer for dental materials and hydroxyl group-containing monomer for dental materials - Google Patents

Description

The present invention relates to a polyfunctional monomer for a dental material, a dental material containing the monomer, a cured product of the dental material, and a kit containing the dental material. The present invention also relates to a hydroxyl group-containing monomer for dental materials, a dental material containing the monomer, a cured product of the dental material, and a kit containing the dental material.

In the clinical setting of dental treatment, the range of use of resin materials is expanding. However, its mechanical properties are not yet sufficient, and in reality, its application to high-stressed parts is limited due to its lack of strength.

Most resin-based dental materials contain monomers that have a (meth) acrylate group in their molecular structure. Typical monomers for dental materials are bisphenol A diglycidyl methacrylate (Bis-GMA), 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (UDMA), and triethylene glycol dimethacrylate (UDMA). TEGDMA) is a dimethacrylate having a methacrylic group at both ends.

In recent years, attempts have been made to improve the mechanical strength of a cured product of a composite resin as a base monomer for dental materials (see, for example, Patent Documents 1 and 2). Some of these compositions are stated to be usable in dental material products in terms of their mechanical properties. Further, in recent years, it has been reported that the strength of a resin for dental materials is improved by introducing a rigid group into a monomer (see, for example, Patent Documents 3 and 4).

Further, it has been reported that it is difficult to completely polymerize the (meth) acrylate group contained in the conventional resin-based dental material, and the polymerization rate reaches only a certain value. (See, for example, Non-Patent Document 1.) The presence of such unpolymerized (meth) acrylate groups is presumed to adversely affect the mechanical properties of the cured product, and the unpolymerized monomer can be eluted from the cured product. It contains sex.

2-Hydroxyethyl methacrylate (hereinafter referred to as HEMA) has a hydroxyl group and a polymerizable group in the molecule, and the hydrophilicity of the molecule derived from the hydroxyl group is considered to be effective for dentin affinity and dentin surface modification. Also, the polymerizable property is effective for integration with the resin matrix. Such properties of HEMA are useful as primers, and are widely blended in the field of dental materials, particularly in dental primers and dental bonding materials (see, for example, Non-Patent Document 2).

In recent years, attempts to improve HEMA have been reported. For example, there is a report that a composition containing a compound in which a part of the hydroxyl group of trehalose is converted into a polymerizable group exhibits high adhesive performance (see, for example, Patent Document 5).

Further, a compound having a sulfonic acid group and a (meth) acrylamide group in the molecule (see, for example, Patent Document 6) and a compound having a hydroxyl group and a (meth) acrylamide group in the molecule (see, for example, Patent Document 7). ) Etc. have been proposed.

Japanese Unexamined Patent Publication No. 2000-204069 Special Table 2013-544823 International release 2015/152220 International Publication 2015/152221 Japanese Unexamined Patent Publication No. 2013-133290 Special Table 2010-505895 Japanese Unexamined Patent Publication No. 2010-150290

Cynthia J.E. Floyd et al., Network structure of Bis-GMA- and UDMA-based resin systems, Dental Materials, 22, 2006, pp.1143-1149 Yoshihiro Nishitani et al., Effect of resin hydrophilicity on dentin adhesion, Adhesive Dentistry, Vol. 26, 2008, pp. 92-98

An object of the present invention is to provide monomers, compositions, dental materials, kits, etc. that are useful for dental materials. Moreover, the object of the 1st aspect and 2nd aspect of this invention is as follows.

In view of the above problems, it is an object of the first aspect of the present invention to provide a polyfunctional monomer for dental materials that gives a cured product having high strength, and a cured product thereof. Another object of the first aspect of the present invention is to provide a dental material containing the polyfunctional monomer for dental materials, which has a low residual rate of unreacted polymerizable ends after curing.
In addition, the actual situation is that further improvement is desired with respect to the adhesiveness to the tooth substance. In view of the above problems, it is an object of the second aspect of the present invention to provide a hydroxyl group-containing monomer for dental materials having a function of improving the adhesive strength with the dentin during dental treatment.

As a result of studies to solve the above problems, the present inventors have produced a (meth) acryloyl group-containing polyfunctional monomer by reacting a polyvalent alcohol or polyol with a (meth) acryloyl group-containing isocyanate compound. What can be done, the cured product of the composition containing the (meth) acryloyl group-containing polyfunctional monomer exhibits high strength, and the composition containing the (meth) acryloyl group-containing polyfunctional monomer is subjected to curing. It was found that a high polymerization rate was exhibited, and the first aspect of the present invention was completed.

In addition, as a result of studies to solve the above problems, the present inventor has found that a hydroxyl group and a (meth) acryloyl group-containing monomer are obtained from the reaction of a polyhydric alcohol or polyol with a (meth) acryloyl group-containing isocyanate compound. We have found that it can be produced and that the adhesiveness of a dental material containing the monomer containing a hydroxyl group and a (meth) acryloyl group to the dentin is improved, and the second aspect of the present invention has been completed.

The first aspect of the present invention includes the matters described in the following [1A] to [23A].
[1A] A polyfunctional monomer for dental materials containing a compound represented by the following general formula (8A) in which the following core portion (X) and the following terminal group (Y2A) are bonded directly or via the following linking group (Z).

（上記一般式（８Ａ）中、ｎ^8aAは核部（Ｘ）に対して直接結合している末端基（Ｙ２Ａ）の数を示し、ｎ^8bAは核部（Ｘ）に対して連結基（Ｚ）を介して結合している末端基（Ｙ２Ａ）の数を示し、ｎ^8aAおよびｎ^8bAの和は核部（Ｘ）の価数に等しく、
核部（Ｘ）は酸素原子または窒素原子を含有し、末端基（Ｙ２Ａ）または連結基（Ｚ）と結合する原子が酸素原子または窒素原子である炭素数１〜２００の３価以上の多価有機基であり、
末端基（Ｙ２Ａ）は、下記一般式（９）で示される（メタ）アクリロイル基含有基（Ｙ３）、（メタ）アクリロイル基、または炭素数１〜２０の炭化水素基であり、複数ある末端基（Ｙ２Ａ）は同一でも異なっていてもよく、ただし、一般式（８Ａ）で示される化合物中のすべての末端基（Ｙ２Ａ）のうち、３以上は（メタ）アクリロイル基含有基（Ｙ３）または（メタ）アクリロイル基でありかつ１以上は（メタ）アクリロイル基含有基（Ｙ３）であり、
連結基（Ｚ）は下記一般式（２）で示される２価の基であり、上記一般式（８Ａ）で示される化合物中に連結基（Ｚ）が複数含まれる場合には、連結基（Ｚ）は同一でも異なっていてもよい。）

(In the above general formula (8A), n ^8aA indicates the number of terminal groups (Y2A) directly bonded to the ^{nuclear portion (X), and n 8bA} indicates the number of linking groups (Z) to the nuclear portion (X). ) Indicates the number of terminal groups (Y2A) ^attached, and the sum of n 8aA and n ^8bA is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y2A) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y2A) is a (meth) acryloyl group-containing group (Y3) represented by the following general formula (9), a (meth) acryloyl group, or a hydrocarbon group having 1 to 20 carbon atoms, and is a plurality of terminal groups. (Y2A) may be the same or different, provided that, of all the terminal groups (Y2A) in the compound represented by the general formula (8A), 3 or more are (meth) acryloyl group-containing groups (Y3) or ( A meta) acryloyl group and one or more are (meth) acryloyl group-containing groups (Y3).
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (8A), the linking group (Z) is used. Z) may be the same or different. )

（上記一般式（９）中、Ｒ^9aは水素原子もしくはメチル基を示し、Ｒ^9bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。）

(In the above general formula (9), R ^9a represents a hydrogen atom or a methyl group, and R ^9b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.)

（上記一般式（２）中、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dの合計は、１〜１００であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合している。）

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2A).)

[2A] The polyfunctional monomer for dental materials according to [1A], wherein the terminal group (Y2A) is a (meth) acryloyl group-containing group (Y3) or a (meth) acryloyl group.
[3A] The polyfunctional monomer for dental materials according to [1A] or [2A], wherein the terminal group (Y2A) is a (meth) acryloyl group-containing group (Y3).
^{[4A] n 2a} , n ^2b , n ^2c , and n ^2d in the linking group (Z) are 0 to 20, respectively ^{, and the total of n 2a} , n ^2b , n ^2c , and n ^2d is 1 to 20. The polyfunctional monomer for dental materials according to any one of [1A] to [3A].
[5A] The polyfunctional monomer for dental materials according to any one of [1A] to [4A], wherein the linking group (Z) is a divalent group represented by the following general formula (4).

（上記一般式（４）中、ｎ^4a、ｎ^4bおよびｎ^4cは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^4a、ｎ^4bおよびｎ^4cの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合している。）

(In the above general formula (4), n ^4a , n ^4b and n ^4c indicate the number of units of each repeating unit, which are 0 to 20, and ^{the total of n 4a} , n ^4b and n ^4c is 1 to 20. The left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2A).)

[6A] The polyfunctional monomer for dental materials according to any one of [1A] to [5A], wherein the linking group (Z) is a divalent group represented by the following general formula (5).

（上記一般式（５）中、ｎ^5aおよびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^5aおよびｎ^5bの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合している。）

(In the above general formula (5), n ^5a and n ^5b indicate the number of units of each repeating unit, which are 0 to 20, respectively, and ^{the total of n 5a} and n ^5b is 1 to 20, which is a group of the above. The left end is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2A).)

[7A] The polyfunctional monomer for dental materials according to any one of [1A] to [6A], wherein the core portion (X) is a 3- to 12-valent organic group.
[8A] Described in any one of [1A] to [7A], wherein the core portion (X) is at least one selected from the group consisting of the groups represented by the following general formulas (6a) to (6j). Polyfunctional monomer for dental materials.

[9A] The (meth) acryloyl group-containing group (Y3) is at least one selected from the group consisting of the groups represented by the following general formulas (9a) to (9f) [1A] to [8A]. The polyfunctional monomer for dental materials according to any one.

[10A] A compound represented by the following general formula (1A) in which the following core portion (X) and the following terminal group (Y1A) are bonded directly or via the following linking group (Z), and the following general formula (3). (Meta) Acryloyl group-containing isocyanate compound represented by) (number of isocyanate groups contained in the compound represented by the following general formula (3)) / (oxygen contained in the compound represented by the following general formula (1A)) A polyfunctional monomer for dental materials, which is a reaction product under the condition that the number of active protons bonded to an atom and a nitrogen atom) = 1.

（上記一般式（１Ａ）中、ｎ^1aAは核部（Ｘ）に直接結合している末端基（Ｙ１Ａ）の数を示し、ｎ^1bAは核部（Ｘ）に連結基（Ｚ）を介して結合している末端基（Ｙ１Ａ）の数を示し、ｎ^1aAおよびｎ^1bAの和は核部（Ｘ）の価数に等しく、
核部（Ｘ）は酸素原子または窒素原子を含有し、末端基（Ｙ１Ａ）または連結基（Ｚ）と結合する原子が酸素原子または窒素原子である炭素数１〜２００の３価以上の多価有機基であり、
末端基（Ｙ１Ａ）は、（メタ）アクリロイル基、炭素数１〜２０の１価の炭化水素基、または水素原子であり、複数あるＹ１Ａは同一でも異なっていてもよく、ただし、上記一般式（１Ａ）で示される化合物中に含まれる末端基（Ｙ１Ａ）のうち３以上は水素原子または（メタ）アクリロイル基であり、かつ１以上は水素原子であり、
連結基（Ｚ）は下記一般式（２）で示される２価の基であり、上記一般式（１Ａ）で示される化合物中に連結基（Ｚ）が複数含まれる場合には、連結基（Ｚ）は同一でも異なっていてもよい。）

(In the above general formula (1A), n ^1aA indicates the number of terminal groups (Y1A) directly bonded to the ^{nuclear portion (X), and n 1bA} indicates the number of terminal groups (Y1A) directly attached to the nuclear portion (X) via a linking group (Z). Indicates the number of bound terminal groups (Y1A), ^{the sum of n 1aA} and n ^1bA is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y1A) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y1A) is a (meth) acryloyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom, and a plurality of Y1A may be the same or different, except that the above general formula (Y1A) Of the terminal groups (Y1A) contained in the compound represented by 1A), 3 or more are hydrogen atoms or (meth) acryloyl groups, and 1 or more are hydrogen atoms.
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (1A), the linking group (Z) is used. Z) may be the same or different. )

（上記一般式（２）中、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dの合計は、１〜１００であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ１Ａ）と結合している。）

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1A).)

（上記一般式（３）中、Ｒ^3aは水素原子またはメチル基を示し、Ｒ^3bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。）

(In the above general formula (3), R ^3a represents a hydrogen atom or a methyl group, and R ^3b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.)

[11A] The polyfunctional monomer for dental materials according to [10A], wherein the terminal group (Y1A) is a hydrogen atom.
^{[12A] n 2a} , n ^2b , n ^2c , and n ^2d in the linking group (Z) are 0 to 20, respectively, and the sum of n ^2a , n ^2b , n ^2c , and n ^2d is 1 to 20. The polyfunctional monomer for dental materials according to [10A] or [11A].
[13A] The polyfunctional monomer for dental materials according to any one of [10A] to [12A], wherein the linking group (Z) is a divalent group represented by the following general formula (4).

（上記一般式（４）中、ｎ^4a、ｎ^4bおよびｎ^4cは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^4a、ｎ^4bおよびｎ^4cの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ１Ａ）と結合している。）

(In the above general formula (4), n ^4a , n ^4b and n ^4c indicate the number of units of each repeating unit, which are 0 to 20, and ^{the total of n 4a} , n ^4b and n ^4c is 1 to 20. The left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1A).)

[14A] The polyfunctional monomer for dental materials according to any one of [10A] to [13A], wherein the linking group (Z) is a divalent group represented by the following general formula (5).

（上記一般式（５）中、ｎ^5aおよびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^5aおよびｎ^5bの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ１Ａ）と結合している。）

(In the above general formula (5), n ^5a and n ^5b indicate the number of units of each repeating unit, which are 0 to 20, respectively, and ^{the total of n 5a} and n ^5b is 1 to 20, which is a group of the above. The left end is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1A).)

[15A] The polyfunctional monomer for dental materials according to any one of [10A] to [14A], wherein the core portion (X) is a 3- to 12-valent organic group.
[16A] The compound (1A) is any one of [10A] to [15A] selected from the group consisting of the compounds represented by the following general formulas (6'a) to (6'k). The polyfunctional monomer for dental materials described in.

（上記一般式（６’ｉ）、（６’ｊ）、および（６’ｋ）中、ｎ^6'i-a、ｎ^6'j-a、およびｎ^6'k-aは、上記核部（Ｘ）に結合するポリオールのアーム数を示し、３以上の整数であり、
上記一般式（６’ｉ）および（６’ｊ）中のｎ^6'i-bおよびｎ^6'j-bは、それぞれオキシエチレン、オキシプロピレンユニットの個数を示し、それぞれ１〜１００の範囲であり、それぞれのアームごとのユニットの個数は同じでも異なっていてもよく、上記一般式（６’ｋ）中のｎ^6'k-bおよびｎ^6'k-cは、それぞれオキシエチレン、オキシプロピレンユニットの個数を示し、その和は１〜１００の範囲であり、それぞれのアームごとのユニットの個数の和は同じでも異なっていてもよい。）

(In the general formulas (6'i), (6'j), and (6'k), n ^6'ia , n ^6'ja , and n ^6'ka bind to the core (X). Indicates the number of arms of the polyol, which is an integer of 3 or more.
^{N 6'ib} and n ^6'jb in the above general formulas (6'i) and (6'j) indicate the number of oxyethylene and oxypropylene units, respectively, and are in the range of 1 to 100, respectively. the number of units per arm may be the same or different, n ^6'Kb and n ^6'Kc in the general formula (6'k), respectively oxyethylene represents the number of oxypropylene units, the sum thereof Is in the range of 1 to 100, and the sum of the number of units for each arm may be the same or different. )

[17A] The (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is at least one selected from the group consisting of the compounds represented by the following general formulas (3a) to (3f) [10A]. The polyfunctional monomer for dental materials according to any one of [16A].

［１８Ａ］ ［１Ａ］〜［１７Ａ］のいずれかに記載の歯科材料用多官能モノマーを含有する歯科材料用モノマー組成物。
［１９Ａ］ 復帰突然変異試験において陰性を示す、［１８Ａ］に記載の歯科材料用モノマー組成物。
［２０Ａ］ ［１Ａ］〜［１７Ａ］のいずれかに記載の歯科材料用多官能モノマーを含有する歯科材料。
［２１Ａ］ 復帰突然変異試験において陰性を示す、［２０Ａ］に記載の歯科材料。
［２２Ａ］ ［２０Ａ］または［２１Ａ］に記載の歯科材料を硬化させてなる硬化物。
［２３Ａ］ ［２０Ａ］または［２１Ａ］に記載の歯科材料を含むキット。

[18A] A monomer composition for dental materials containing the polyfunctional monomer for dental materials according to any one of [1A] to [17A].
[19A] The monomer composition for dental materials according to [18A], which is negative in the reversion mutation test.
[20A] A dental material containing the polyfunctional monomer for dental materials according to any one of [1A] to [17A].
[21A] The dental material according to [20A], which is negative in the reversion mutation test.
[22A] A cured product obtained by curing the dental material according to [20A] or [21A].
[23A] A kit containing the dental material according to [20A] or [21A].

The second aspect of the present invention includes the matters described in the following [1B] to [21B].
[1B] A hydroxyl group-containing monomer for dental materials containing a compound represented by the following general formula (8B) in which the following core portion (X) and the following terminal group (Y2B) are bonded directly or via the following linking group (Z).

（上記一般式（８Ｂ）中、ｎ^8aBは核部（Ｘ）に対して直接結合している末端基（Ｙ２Ｂ）の数を示し、ｎ^8bBは核部（Ｘ）に対して連結基（Ｚ）を介して結合している末端基（Ｙ２Ｂ）の数を示し、ｎ^8aBおよびｎ^8bBの和は核部（Ｘ）の価数に等しく、
核部（Ｘ）は酸素原子または窒素原子を含有し、末端基（Ｙ２Ｂ）または連結基（Ｚ）と結合する原子が酸素原子または窒素原子である炭素数１〜２００の３価以上の多価有機基であり、
末端基（Ｙ２Ｂ）は、下記一般式（９）で示される（メタ）アクリロイル基含有基（Ｙ３）、（メタ）アクリロイル基、炭素数１〜２０の炭化水素基、または水素原子であり、複数ある末端基（Ｙ２Ｂ）は同一でも異なっていてもよく、ただし、一般式（８Ｂ）で示される化合物中のすべての末端基（Ｙ２Ｂ）のうち、１以上は（メタ）アクリロイル基含有基（Ｙ３）でありかつ１以上は水素原子であり、
連結基（Ｚ）は下記一般式（２）で示される２価の基であり、上記一般式（８Ｂ）で示される化合物中に連結基（Ｚ）が複数含まれる場合には、連結基（Ｚ）は同一でも異なっていてもよい。）

(In the above general formula (8B), n ^8aB indicates the number of terminal groups (Y2B) directly bonded to the ^{nuclear portion (X), and n 8bB} indicates the number of linking groups (Z) to the nuclear portion (X). ) Is shown, ^{and the sum of n 8aB} and n ^8bB is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y2B) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y2B) is a (meth) acryloyl group-containing group (Y3) represented by the following general formula (9), a (meth) acryloyl group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom. Certain end groups (Y2B) may be the same or different, except that one or more of all end groups (Y2B) in the compound represented by the general formula (8B) are (meth) acryloyl group-containing groups (Y3). ) And 1 or more are hydrogen atoms,
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (8B), the linking group (Z) is used. Z) may be the same or different. )

（上記一般式（９）中、Ｒ^9aは水素原子もしくはメチル基を示し、Ｒ^9bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。）

(In the above general formula (9), R ^9a represents a hydrogen atom or a methyl group, and R ^9b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.)

（上記一般式（２）中、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dの合計は、１〜１００であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ｂ）と結合している。）

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2B).)

[2B] The hydroxyl group-containing monomer for dental materials according to [1B], wherein the terminal group (Y2B) is a (meth) acryloyl group-containing group (Y3) or a hydrogen atom.
^{[3B] n 2a} , n ^2b , n ^2c , and n ^2d in the linking group (Z) are 0 to 20, respectively, and the sum of n ^2a , n ^2b , n ^2c , and n ^2d is 1 to 20. The hydroxyl group-containing monomer for dental materials according to [1B] or [2B].
[4B] The hydroxyl group-containing monomer for dental materials according to any one of [1B] to [3B], wherein the linking group (Z) is a divalent group represented by the following general formula (4).

（上記一般式（４）中、ｎ^4a、ｎ^4bおよびｎ^4cは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^4a、ｎ^4bおよびｎ^4cの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ｂ）と結合している。）

(In the above general formula (4), n ^4a , n ^4b and n ^4c indicate the number of units of each repeating unit, which are 0 to 20, and ^{the total of n 4a} , n ^4b and n ^4c is 1 to 20. The left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2B).)

[5B] The hydroxyl group-containing monomer for dental materials according to any one of [1B] to [4B], wherein the linking group (Z) is a divalent group represented by the following general formula (5).

（上記一般式（５）中、ｎ^5aおよびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^5aおよびｎ^5bの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ｂ）と結合している。）

(In the above general formula (5), n ^5a and n ^5b indicate the number of units of each repeating unit, which are 0 to 20, respectively, and ^{the total of n 5a} and n ^5b is 1 to 20, which is a group of the above. The left end is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2B).)

[6B] The hydroxyl group-containing monomer for dental materials according to any one of [1B] to [5B], wherein the core portion (X) is a 3- to 12-valent organic group.
[7B] Described in any one of [1B] to [6B], wherein the core portion (X) is at least one selected from the group consisting of the groups represented by the following general formulas (6a) to (6j). Hydroxy group-containing monomer for dental materials.

[8B] The (meth) acryloyl group-containing group (Y3) is at least one selected from the group consisting of the groups represented by the following general formulas (9a) to (9f) [1B] to [7B]. The hydroxyl group-containing monomer for dental materials according to any one.

[9B] A compound represented by the following general formula (1B) in which the following core portion (X) and the following terminal group (Y1B) are bonded directly or via the following linking group (Z), and the following general formula (3). ) ≤ (1 / number of active protons bonded to oxygen and nitrogen atoms contained in the compound represented by the following general formula (1B)) with the (meth) acryloyl group-containing isocyanate compound represented by the following general formula (3). ) / (Number of active protons bonded to oxygen and nitrogen atoms contained in the compound represented by the following general formula (1B)) <Reaction product under the condition of <1 A hydroxyl compound-containing monomer for dental materials.

（上記一般式（１Ｂ）中、ｎ^1aBは核部（Ｘ）に直接結合している末端基（Ｙ１Ｂ）の数を示し、ｎ^1bBは核部（Ｘ）に連結基（Ｚ）を介して結合している末端基（Ｙ１Ｂ）の数を示し、ｎ^1aBおよびｎ^1bBの和は核部（Ｘ）の価数に等しく、
核部（Ｘ）は酸素原子または窒素原子を含有し、末端基（Ｙ１Ｂ）または連結基（Ｚ）と結合する原子が酸素原子または窒素原子である炭素数１〜２００の３価以上の多価有機基であり、
末端基（Ｙ１Ｂ）は、（メタ）アクリロイル基、炭素数１〜２０の１価の炭化水素基、または水素原子であり、複数あるＹ１Ｂは同一でも異なっていてもよく、ただし、上記一般式（１Ｂ）で示される化合物中に含まれる末端基（Ｙ１Ｂ）のうち２以上は水素原子であり、
連結基（Ｚ）は下記一般式（２）で示される２価の基であり、上記一般式（１Ｂ）で示される化合物中に連結基（Ｚ）が複数含まれる場合には、連結基（Ｚ）は同一でも異なっていてもよい。）

(In the above general formula (1B), n ^1aB indicates the number of terminal groups (Y1B) directly bonded to the ^{nuclear portion (X), and n 1bB} indicates the number of terminal groups (Y1B) directly attached to the nuclear portion (X) via a linking group (Z). Indicates the number of bound terminal groups (Y1B), ^{the sum of n 1aB} and n ^1bB is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group ( Y1B ) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y1B) is a (meth) acryloyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom, and a plurality of Y1Bs may be the same or different, except that the above general formula (Y1B) Two or more of the terminal groups (Y1B) contained in the compound represented by 1B) are hydrogen atoms.
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (1B), the linking group (Z) is used. Z) may be the same or different. )

（上記一般式（２）中、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dの合計は、１〜１００であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ１Ｂ）と結合している。）

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1B).)

（上記一般式（３）中、Ｒ^3aは水素原子またはメチル基を示し、Ｒ^3bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。）

(In the above general formula (3), R ^3a represents a hydrogen atom or a methyl group, and R ^3b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.)

[10B] The hydroxyl group-containing monomer for dental materials according to [9B], wherein the terminal group (Y1B) is a hydrogen atom.
^{[11B] n 2a} , n ^2b , n ^2c , and n ^2d in the linking group (Z) are 0 to 20, respectively, and the sum of n ^2a , n ^2b , n ^2c , and n ^2d is 1 to 20. The hydroxyl group-containing monomer for dental materials according to [9B] or [10B].
[12B] The hydroxyl group-containing monomer for dental materials according to any one of [9B] to [11B], wherein the linking group (Z) is a divalent group represented by the following general formula (4).

（上記一般式（４）中、ｎ^4a、ｎ^4bおよびｎ^4cは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^4a、ｎ^4bおよびｎ^4cの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ１Ｂ）と結合している。）

(In the above general formula (4), n ^4a , n ^4b and n ^4c indicate the number of units of each repeating unit, which are 0 to 20, and ^{the total of n 4a} , n ^4b and n ^4c is 1 to 20. The left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1B).)

[13B] The hydroxyl group-containing monomer for dental materials according to any one of [9B] to [12B], wherein the linking group (Z) is a divalent group represented by the following general formula (5).

（上記一般式（５）中、ｎ^5aおよびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ０〜２０であり、ｎ^5aおよびｎ^5bの合計は、１〜２０であり、上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ１Ｂ）と結合している。）
［１４Ｂ］上記核部（Ｘ）が、３〜１２価の有機基である［９Ｂ］〜［１３Ｂ］のいずれかに記載の歯科材料用水酸基含有モノマー。
［１５Ｂ］上記化合物（１Ｂ）が、下記一般式（６’ａ）〜（６’ｋ）で示される化合物からなる群より選択される少なくとも１つである［９Ｂ］〜［１４Ｂ］のいずれかに記載の歯科材料用水酸基含有モノマー。

(In the above general formula (5), n ^5a and n ^5b indicate the number of units of each repeating unit, which are 0 to 20, respectively, and ^{the total of n 5a} and n ^5b is 1 to 20, which is a group of the above. The left end is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1B).)
[14B] The hydroxyl group-containing monomer for dental materials according to any one of [9B] to [13B], wherein the core portion (X) is a 3- to 12-valent organic group.
[15B] Any one of [9B] to [14B], wherein the compound (1B) is at least one selected from the group consisting of compounds represented by the following general formulas (6'a) to (6'k). The hydroxyl group-containing monomer for dental materials according to.

（上記一般式（６’ｉ）、（６’ｊ）、および（６’ｋ）中、ｎ^6'i-a、ｎ^6'j-a、およびｎ^6'k-aは、上記核部Ｘに結合するポリオールのアーム数を示し、３以上の整数であり、
上記一般式（６’ｉ）および（６’ｊ）中のｎ^6'i-bおよびｎ^6'j-bは、それぞれオキシエチレン、オキシプロピレンユニットの個数を示し、それぞれ１〜１００の範囲であり、それぞれのアームごとのユニットの個数は同じでも異なっていてもよく、上記一般式（６’ｋ）中のｎ^6'k-bおよびｎ^6'k-cは、それぞれオキシエチレン、オキシプロピレンユニットの個数を示し、その和は１〜１００の範囲であり、それぞれのアームごとのユニットの個数の和は同じでも異なっていてもよい。）

(In the general formulas (6'i), (6'j), and (6'k), n ^6'ia , n ^6'ja , and n ^6'ka are the polyols that bind to the core X. Indicates the number of arms and is an integer of 3 or more.
^{N 6'ib} and n ^6'jb in the above general formulas (6'i) and (6'j) indicate the number of oxyethylene and oxypropylene units, respectively, and are in the range of 1 to 100, respectively. the number of units per arm may be the same or different, n ^6'Kb and n ^6'Kc in the general formula (6'k), respectively oxyethylene represents the number of oxypropylene units, the sum thereof Is in the range of 1 to 100, and the sum of the number of units for each arm may be the same or different. )

[16B] The (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is at least one selected from the group consisting of the compounds represented by the following general formulas (3a) to (3f) [9B]. The hydroxyl group-containing monomer for dental materials according to any one of [15B].

［１７Ｂ］［１Ｂ］〜［１６Ｂ］のいずれかに記載の歯科材料用水酸基含有モノマーを含有する歯科材料用モノマー組成物。
［１８Ｂ］復帰突然変異試験において陰性を示す、［１７Ｂ］に記載の歯科材料用モノマー組成物。
［１９Ｂ］［１Ｂ］〜［１６Ｂ］のいずれかに記載の歯科材料用水酸基含有モノマーを含有する歯科材料。
［２０Ｂ］復帰突然変異試験において陰性を示す、［１９Ｂ］に記載の歯科材料。
［２１Ｂ］［１９Ｂ］または［２０Ｂ］に記載の歯科材料を含むキット。

[17B] The monomer composition for dental materials containing the hydroxyl group-containing monomer for dental materials according to any one of [1B] to [16B].
[18B] The monomer composition for dental materials according to [17B], which is negative in the reversion mutation test.
[19B] The dental material containing the hydroxyl group-containing monomer for dental materials according to any one of [1B] to [16B].
[20B] The dental material according to [19B], which is negative in the reversion mutation test.
[21B] A kit containing the dental material according to [19B] or [20B].

The monomer obtained in the present invention is useful as a dental material.
By curing the composition containing the polyfunctional monomer for dental materials according to the first aspect of the present invention, a cured product having high strength can be obtained. Further, the dental material containing the polyfunctional monomer for dental materials has a low residual rate of unreacted polymerizable ends after curing.
The hydroxyl group-containing monomer for dental materials, which is the second aspect of the present invention, has a function of improving the adhesive strength with the dentin during dental treatment.

Hereinafter, the present invention will be described in detail. In the present specification, "(meth) acrylic" means acrylic or methacrylic, and for example, "(meth) acrylic acid" means methacrylic acid or acrylic acid. Similarly, "(meth) acryloyl" means "acryloyl" or "methacryloyl", and "(meth) acrylate" means "acrylate" or "methacrylate".

[Polyfunctional monomer for dental materials]
The polyfunctional monomer for dental materials according to the first aspect of the present invention has the following general formula (8A) in which the following core portion (X) and the following terminal group (Y2A) are bonded directly or via the following linking group (Z). It is a compound indicated by.

上記一般式（８Ａ）中、ｎ^8aAは核部（Ｘ）に対して直接結合している末端基（Ｙ２Ａ）の数を示し、ｎ^8bAは核部（Ｘ）に対して連結基（Ｚ）を介して結合している末端基（Ｙ２Ａ）の数を示し、ｎ^8aAおよびｎ^8bAの和は核部（Ｘ）の価数に等しい。ｎ^8aAおよびｎ^8bAは０以上の整数であり、その和が３以上であればその組み合わせには特に制限がない。組み合わせの一例としては、ｎ^8aAが０であれば、ｎ^8bAは３以上の整数となり、この場合は、全ての末端基（Ｙ２Ａ）は核部Ｘに連結基（Ｚ）を介して結合している。また、別の組み合わせの一例としては、ｎ^8bAが０であれば、ｎ^8aAは３以上の整数となり、この場合は、全ての末端基（Ｙ２Ａ）は核部Ｘに直接結合している。

In the above general formula (8A), n ^8aA indicates the number of terminal groups (Y2A) directly bonded to the ^{nucleus (X), and n 8bA} is the linking group (Z) to the nucleus (X). Indicates the number of terminal groups (Y2A) attached via, ^{and the sum of n 8aA} and n ^8bA is equal to the valence of the nucleus (X). n ^8aA and n ^8bA are integers of 0 or more, and the combination is not particularly limited as long as the sum is 3 or more. As an example of the combination ^{, if n 8aA} is 0, n ^8bA is an integer of 3 or more. In this case, all the terminal groups (Y2A) are bonded to the core X via the linking group (Z). There is. Further, as an example of another combination ^{, if n 8bA} is 0, n ^8aA is an integer of 3 or more, and in this case, all the end groups (Y2A) are directly bonded to the nuclear portion X.

[Nuclear part (X)]
The core portion (X) is a trivalent or higher valent organic group containing an oxygen atom or a nitrogen atom and the atom bonded to the terminal group (Y2A) or the linking group (Z) is an oxygen atom or a nitrogen atom. .. The oxygen atom or nitrogen atom bonded to the terminal group (Y2A) or the linking group (Z) is a methylene group or a divalent aromatic carbon group other than the terminal group (Y2A) or the linking group (Z). It is combined. Any hydrogen atom contained in the methylene group or the divalent aromatic carbon group may be replaced with a monovalent hydrocarbon group having 1 to 12 carbon atoms. The number of carbon atoms in the core portion (X) is usually in the range of 1 to 200, but is preferably 1 to 100, more preferably 1 to 30, and even more preferably 2 to 20.

The valence of the core portion (X) is 3 or more as described above, but is preferably 3 to 12 valences, and more preferably 3 to 8 valences. The atom bonded to the terminal group (Y2A) or the linking group (Z) is selected from an oxygen atom or a nitrogen atom as described above, but is preferably an oxygen atom. Examples of the core portion (X) include groups represented by the following general formulas (6a) to (6j).

なお、上記一般式（６ｇ）中のｎ^6gは、１〜４０の整数であり、１〜２０であることが好ましく、１〜１０であることがより好ましく、１〜５であることがさらに好ましい。

^{In addition, n 6g} in the general formula (6g) is an integer of 1 to 40, preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5. ..

[Terminal group (Y2A)]
The terminal group (Y2A) is a (meth) acryloyl group-containing group (Y3) represented by the following general formula (9), a (meth) acryloyl group, or a hydrocarbon group having 1 to 20 carbon atoms, and is a plurality of terminal groups. (Y2A) may be the same or different, provided that, of all the terminal groups (Y2A) in the compound represented by the general formula (8A), 3 or more are (meth) acryloyl group-containing groups (Y3) or ( It is a (meth) acryloyl group and one or more are (meth) acryloyl group-containing groups (Y3).

上記一般式（９）中、Ｒ^9aは水素原子もしくはメチル基を示し、Ｒ^9bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。上記一般式（９）で示される（メタ）アクリロイル基含有基（Ｙ３）としては、例えば、下記一般式（９ａ）〜（９ｆ）で示される基が挙げられる。

In the above general formula (9), R ^9a represents a hydrogen atom or a methyl group, and R ^9b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group. Examples of the (meth) acryloyl group-containing group (Y3) represented by the general formula (9) include groups represented by the following general formulas (9a) to (9f).

末端基（Ｙ２Ａ）は、上述のように上記一般式（９）で示される（メタ）アクリロイル基含有基（Ｙ３）、（メタ）アクリロイル基、または炭素数１〜２０の炭化水素基であるが、（メタ）アクリロイル基含有基（Ｙ３）または（メタ）アクリロイル基であることが好ましく、（メタ）アクリロイル基含有基（Ｙ３）であることがより好ましい。

The terminal group (Y2A) is a (meth) acryloyl group-containing group (Y3) represented by the above general formula (9), a (meth) acryloyl group, or a hydrocarbon group having 1 to 20 carbon atoms as described above. , (Meta) acryloyl group-containing group (Y3) or (meth) acryloyl group is preferable, and (meth) acryloyl group-containing group (Y3) is more preferable.

[Connecting group (Z)]
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (8A), the linking group (Z) is used. Z) may be the same or different.

上記一般式（２）中、ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、好ましくは０〜２０である。ｎ^2a、ｎ^2b、ｎ^2c、およびｎ^2dの合計は、１〜１００であり、好ましくは１〜２０である。上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合している。

In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, and are 0 to 100, preferably 0 to 20, respectively. The sum of n ^2a , n ^2b , n ^2c , and n ^2d is 1 to 100, preferably 1 to 20. The left end of the group is bound to the nucleus (X) and the right end of the group is bound to the terminal group (Y2A).

_{The repeating unit represented by −C 2} H ₄ O − in the general formula (2) is an oxyethylene unit. Examples of the oxyethylene unit include -CH ₂ CH ₂ O- and -CH (CH ₃ ) O-. Among these oxyethylene units, −CH ₂ CH ₂ O− is preferable. These oxyethylene units may be contained alone or in combination of two or more.

Repeating unit represented -C ₃ H ₆ O- in in the general formula (2) is a oxypropylene units. Examples of the oxypropylene units, _{e.g., -CH 2 CH 2 CH 2 O} -, - CH (CH 3) CH 2 O-, and -CH ₂ CH (CH ₃₎ groups such as O- and the like. Among these oxypropylene units, −CH (CH ₃ ) CH ₂ O− and −CH ₂ CH (CH ₃ ) O− are preferable. These oxypropylene units may be contained alone or in combination of two or more.

Repeating unit represented -C ₄ H ₈ O- in the formula (2) in is the oxybutylene units. Examples of the oxybutylene unit include −CH ₂ CH ₂ CH ₂ CH ₂ O−, −CH (CH ₃ ) CH ₂ CH ₂ O−, −CH ₂ CH (CH ₃ ) CH ₂ O−, −CH ₂ CH ₂ CH (CH ₃ ) O-, -CH (CH ₂ CH ₃ ) CH ₂ O-, -CH ₂ CH (CH ₂ CH ₃ ) O-, -CH (CH ₃ ) CH (CH ₃ ) O-, Groups such as −C (CH ₃ ) ₂ CH ₂ O− and −CH ₂ C (CH ₃ ) ₂ O− can be mentioned. Among these oxybutylene units, −CH ₂ CH ₂ CH ₂ CH ₂ O− is preferable. These oxybutylene units may be contained alone or in combination of two or more.

_{The repeating unit represented by −CO (CH 2} ) ₅ O− in the above general formula (2) is one unit of the polycaprolactone chain.
The above repeating unit may be composed of one type or two or more types. When two or more kinds of repeating units are included, there is no particular limitation on the form in which these repeating units are included. For example, each repeating unit may be randomly included, or a certain number of repeating units are solidified. That is, each repeating unit may be included in a block manner. Moreover, the order of these repeating units is not limited in any way.

The linking group (Z) is preferably a divalent group represented by the following general formula (4). When a plurality of linking groups (Z) are contained in the compound represented by the general formula (8A), the linking groups (Z) may be the same or different.

上記一般式（４）中、ｎ^4a、ｎ^4bおよびｎ^4cは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、好ましくは０〜２０である。ｎ^4a、ｎ^4bおよびｎ^4cの合計は、１〜１００であり、好ましくは１〜２０である。上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合している。上記一般式（４）中の各繰り返し単位に関する説明は、上記一般式（２）中の各繰り返し単位の説明と同一である。

In the above general formula (4), n ^4a , n ^4b and n ^4c indicate the number of units of each repeating unit, which is 0 to 100, preferably 0 to 20 respectively. The sum of n ^4a , n ^4b and n ^4c is 1 to 100, preferably 1 to 20. The left end of the group is bound to the nucleus (X) and the right end of the group is bound to the terminal group (Y2A). The description of each repeating unit in the general formula (4) is the same as the description of each repeating unit in the general formula (2).

The linking group (Z) is more preferably a divalent group represented by the following general formula (5). When a plurality of linking groups (Z) are contained in the compound represented by the general formula (8A), the linking groups (Z) may be the same or different.

上記一般式（５）中、ｎ^5aおよびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ０〜１００であり、好ましくは０〜２０である。ｎ^5aおよびｎ^5bの合計は、１〜１００であり、好ましくは１〜２０である。上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合している。上記一般式（５）中の各繰り返し単位に関する説明は、上記一般式（２）中の各繰り返し単位の説明と同一である。

In the above general formula (5), n ^5a and n ^5b indicate the number of units of each repeating unit, which are 0 to 100, preferably 0 to 20 respectively. The sum of n ^5a and n ^5b is 1 to 100, preferably 1 to 20. The left end of the group is bound to the nucleus (X) and the right end of the group is bound to the terminal group (Y2A). The description of each repeating unit in the general formula (5) is the same as the description of each repeating unit in the general formula (2).

As a more specific example of the linking group (Z), the repeating unit is composed of only the oxyethylene unit (in the general formula (5), n ^5b is 0, n ^5a is 1 to 100, preferably 1 to 100. 1 to 20), those composed only of oxypropylene units (in the general formula (5), n ^5a is 0, n ^5b is 1 to 100, preferably 1 to 20), oxy Polymer block composed of propylene unit-Polymer block composed of oxyethylene unit-Polymer block composed of oxypropylene unit has a block structure (in the general formula (5), it is connected by the structure of the following (5'). Those with a structure that has been modified) can be mentioned.

上記一般式（５’）中、ｎ^5a1、ｎ^5a2およびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ１〜１００であり、好ましくは１〜２０である。ｎ^5a1、ｎ^5a2およびｎ^5bの合計は、１〜１００であり、好ましくは１〜２０である。上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ａ）と結合しており、括弧内のオキシプロピレン重合体ブロック、オキシエチレン重合体ブロックはこの順に結合している。上記一般式（５’）中の各繰り返し単位に関する説明は、上記一般式（２）中の各繰り返し単位の説明と同一である。

In the above general formula (5'), n ^5a1 , n ^5a2, and n ^5b indicate the number of units of each repeating unit, which is 1 to 100, preferably 1 to 20, respectively. The sum of n ^5a1 , n ^5a2 and n ^5b is 1 to 100, preferably 1 to 20. The left end of the group is bonded to the nucleus (X), the right end of the group is bonded to the terminal group (Y2A), and the oxypropylene polymer block and the oxyethylene polymer block in parentheses are bonded in this order. doing. The description of each repeating unit in the general formula (5') is the same as the description of each repeating unit in the general formula (2).

[Manufacturing method of polyfunctional monomer for dental materials]
The polyfunctional monomer for dental materials of the present invention has, for example, the following general formula (1A) in which the following core portion (X) and the following terminal group (Y1A) are bonded directly or via the following linking group (Z). It is obtained by reacting all the active protons in the compound shown with the isocyanate group in the (meth) acryloyl group-containing isocyanate compound represented by the following general formula (3) to form the corresponding carbamate group or urea group. .. The active proton referred to here refers to a hydrogen atom that binds to alcoholic oxygen and amine nitrogen and has reactivity with isocyanate at a practical rate.

The conditions for producing the polyfunctional monomer for dental materials of the present invention are, for example, the following general formula in which the following core portion (X) and the following terminal group (Y1A) are bonded directly or via the following linking group (Z). The isocyanate group contained in the compound represented by the following general formula (3) of the raw material containing the compound represented by 1A) and the raw material containing the (meth) acryloyl group-containing isocyanate compound represented by the following general formula (3). (Number of moles) / (Number of moles of active protons bonded to oxygen and nitrogen atoms contained in the compound represented by the following general formula (1A)) (hereinafter referred to as the reaction ratio at the time of production) = 1. It is a reaction.

Further, as another example, there is a reaction under the condition that the reaction ratio at the time of production> 1. In this case, in terms of stoichiometric ratio, the (meth) acryloyl group-containing isocyanate compound represented by the following general formula (3) remains, but all the activities in the compound represented by the following general formula (1A) remain. Protons can react with isocyanate groups to give mixtures containing the polyfunctional monomers for dental materials of the invention. The reaction ratio at the time of the above production is preferably close to 1, but is preferably 2, for example, preferably 1.5 or less, and more preferably 1.2 or less. Such a mixture can also be blended with the dental material of the present invention directly or by undergoing a known reaction or treatment as it is.

Further, as another example, there is a reaction under the condition of the reaction ratio <1 at the time of production. In this case, in terms of stoichiometric ratio, a part of the active protons in the compound represented by the following general formula (1A) will remain in the reaction product, but the reaction ratio at the time of the above production is a certain amount or more. If so, a mixture containing the polyfunctional monomer for dental materials of the present invention can be obtained. In order to improve the ratio of the polyfunctional monomer for dental materials of the present invention in the mixture, the reaction ratio at the time of production is preferably close to 1, for example, ((average number of active protons in one molecule-1). ) / (Average number of active protons in one molecule)) or more. Such a mixture can also be blended with the dental material of the present invention directly or by undergoing a known reaction or treatment as it is.

The number of moles of active protons in a raw material containing a compound represented by the following general formula (1A) is determined by a known analysis method, for example, measurement of hydroxyl value, specifically JIS K 0070-1992, JIS K 1557-1-2007. , ISO 14900-2001 and methods conforming to these, etc., can be obtained by calculation. The number of moles of isocyanate groups contained in the compound represented by the following general formula (3) is determined by a known analysis method, for example, measurement of NCO value, specifically JIS K 7301-1995, JIS K 1603-2007, JIS. It can be obtained by calculation from K 1556-2006, ISO 14896-2006 and methods conforming to these.

上記一般式（１Ａ）中、ｎ^1aAは核部（Ｘ）に直接結合している末端基（Ｙ１Ａ）の数を示し、ｎ^1bAは核部（Ｘ）に連結基（Ｚ）を介して結合している末端基（Ｙ１Ａ）の数を示し、ｎ^1aAおよびｎ^1bAの和は、核部（Ｘ）の価数に等しい。ｎ^1aAおよびｎ^1bAは０以上の整数であり、その和が３以上であればその組み合わせには特に制限がない。組み合わせの一例としては、ｎ^1aAが０であれば、ｎ^1bAは３以上の整数となり、この場合は、全ての末端基（Ｙ１Ａ）は核部Ｘに連結基（Ｚ）を介して結合している。また、別の組み合わせの一例としては、ｎ^1bAが０であれば、ｎ^1aAは３以上の整数となり、この場合は、全ての末端基（Ｙ２Ａ）は核部Ｘに直接結合している。核部（Ｘ）および連結基（Ｚ）の説明は、上述一般式（８Ａ）に対する説明のとおりである。

In the above general formula (1A), n ^1aA indicates the number of terminal groups (Y1A) directly attached to the ^{nucleus (X), and n 1bA} is attached to the nucleus (X) via a linking group (Z). The number of terminal groups (Y1A) is shown, ^{and the sum of n 1aA} and n ^1bA is equal to the valence of the nucleus (X). n ^1aA and n ^1bA are integers of 0 or more, and the combination is not particularly limited as long as the sum is 3 or more. As an example of the combination ^{, if n 1aA} is 0, n ^1bA is an integer of 3 or more. In this case, all the terminal groups (Y1A) are bonded to the core X via the linking group (Z). There is. Further, as an example of another combination ^{, if n 1bA} is 0, n ^1aA is an integer of 3 or more, and in this case, all the end groups (Y2A) are directly bonded to the nuclear portion X. The description of the core portion (X) and the linking group (Z) is as described with respect to the above general formula (8A).

[Terminal group (Y1A)]
The terminal group (Y1A) is a (meth) acryloyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom, and a plurality of Y1A may be the same or different. However, 3 or more of the terminal groups (Y1A) contained in the compound represented by the above general formula (1A) are hydrogen atoms or (meth) acryloyl groups, and 1 or more are hydrogen atoms. The terminal group (Y1A) is preferably a (meth) acryloyl group or a hydrogen atom, and more preferably composed of only a hydrogen atom.

[Specific example of the compound of the general formula (1A)]
Examples of the compound of the general formula (1A) include polyols represented by the following general formulas (6'a) to (6'h).

なお、上記一般式（６’ｇ）中のｎ^6'gは、１〜４０の整数であり、１〜２０であることが好ましく、１〜１０であることがより好ましく、１〜５であることがさらに好ましい。

^{In addition, n 6'g} in the above general formula (6'g) is an integer of 1 to 40, preferably 1 to 20, more preferably 1 to 10, and 1 to 5. Is even more preferable.

Further, as another example of the compound of the general formula (1A), for example, the polyols represented by the following general formulas (6'i) to (6'k) can be mentioned.

上記一般式（６’ｉ）、（６’ｊ）、および（６’ｋ）中のｎ^6'i-a、ｎ^6'j-a、およびｎ^6'k-aは、上記核部（Ｘ）に結合するポリオールのアーム数を示し、本発明においては、３以上の整数であるが、３〜１２であることが好ましく、３〜８であることがより好ましい、３〜６であることがさらに好ましい。上記一般式（６’ｉ）および（６’ｊ）中のｎ^6'i-bおよびｎ^6'j-bは、それぞれオキシエチレン単位、オキシプロピレン単位の個数を示し、それぞれ１〜１００の範囲であり、１〜２０であることが好ましく、それぞれのアームごとの繰り返し単位の個数は同じでも異なっていてもよい。上記一般式（６’ｋ）中のｎ^6'k-bおよびｎ^6'k-cは、それぞれオキシエチレン単位、オキシプロピレン単位の個数を示し、その和は１〜１００の範囲であり、１〜２０であることが好ましく、それぞれのアームごとの繰り返し単位の個数の和は同じでも異なっていてもよい。上記一般式（６’ｉ）、（６’ｊ）、および（６’ｋ）中のＸは核部（Ｘ）であり、その例としては、上記一般式（６ａ）〜（６ｈ）で示される基からなる群より選ばれる少なくとも１つの基である。

^{The n 6'ia} , n ^6'ja , and n ^6'ka in the general formulas (6'i), (6'j), and (6'k) are polyols that bind to the core (X). In the present invention, it is an integer of 3 or more, preferably 3 to 12, more preferably 3 to 8, and even more preferably 3 to 6. ^{N 6'ib} and n ^6'jb in the above general formulas (6'i) and (6'j) indicate the number of oxyethylene units and oxypropylene units, respectively, and are in the range of 1 to 100, respectively. It is preferably ~ 20, and the number of repeating units for each arm may be the same or different. ^{N 6'kb} and n ^6'kc in the above general formula (6'k) indicate the number of oxyethylene units and oxypropylene units, respectively, and the sum thereof is in the range of 1 to 100 and is 1 to 20. It is preferable that the sum of the number of repeating units for each arm may be the same or different. X in the general formulas (6'i), (6'j), and (6'k) is the core portion (X), and examples thereof are shown in the general formulas (6a) to (6h). It is at least one group selected from the group consisting of the groups.

Some polyols having repeating units such as oxyethylene units and oxypropylene units in the molecule have already been widely used in the industrial world as materials for polyurethane and the like. The production method is not particularly limited, but it can be obtained by adding ethylene oxide, propylene oxide or the like to the polyols represented by the general formulas (6'a) to (6'h) by a known method.

[(Meta) acryloyl group-containing isocyanate compound]

上記一般式（３）中、Ｒ^3aは水素原子またはメチル基を示し、Ｒ^3bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。

In the above general formula (3), R ^3a represents a hydrogen atom or a methyl group, and R ^3b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.

As a specific example of the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3), at least one selected from the group consisting of the compounds represented by the following general formulas (3a) to (3f) is selected. Can be mentioned.

これらの（メタ）アクリロイル基含有イソシアネート化合物は、１種単独で用いてもよいし、２種以上混合して用いてもよい。

These (meth) acryloyl group-containing isocyanate compounds may be used alone or in admixture of two or more.

[Reaction conditions]
The polyfunctional monomer for dental materials of the present invention can be obtained by reacting the compound represented by the above general formula (1A) with the (meth) acryloyl group-containing isocyanate compound represented by the above general formula (3) as described above. However, the reaction can be carried out by a known or known method.

For example, the polyfunctional monomer for dental materials of the present invention can be obtained by mixing the compound represented by the general formula (1A) with the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). it can. At this time, the hydroxyl group or amino group in the compound represented by the general formula (1A) reacts with the isocyanate group in the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) to form a carbamoyl group. Alternatively, a urea group is generated. Such a reaction is sometimes called a urethanization reaction.

At the time of the reaction, a catalyst may or may not be added, but it is preferable to add a catalyst in order to improve the reaction rate. As the catalyst, a known catalyst that accelerates the urethanization reaction can be used.

Examples of the urethanization catalyst include organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate and tin octanoate, copper naphthenate, cobalt naphthenate, zinc naphthenate, acetylacetonatozirconium, acetylacetonato iron and acetylacetonato. Other organic metal compounds other than tin, such as germanium, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1-diazabicyclo [2.2.2] octane, 1, 8-diazabicyclo [5.4.0] undecene, N, N-dimethylcyclohexylamine, pyridine, N-methylmorpholin, N, N, N', N'-tetramethylethylenediamine, N, N, N', N' -Tetramethyl-1,3-butanediamine, N, N, N', N'-pentamethyldiethylenetriamine, N, N, N', N'-tetra (3-dimethylaminopropyl) -methanediamine, N, N Amine compounds such as'-dimethylpiperazine and 1,2-dimethylimidazole and salts thereof, trialkylphosphine compounds such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine and tri-n-octylphosphine. And so on.
Among these, dibutyltin dilaurate and tin octanate, which proceed with the reaction in a small amount and have high selectivity for the diisocyanate compound, are preferable.

When a urethanization catalyst is used, the total weight of the compound represented by the general formula (1A) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is 100 parts by weight. It is preferable to add 001 to 0.5 parts by weight, more preferably 0.002 to 0.3 parts by weight, further preferably 0.01 to 0.3 parts by weight, and 0. It is more preferable to add 01 to 0.2 parts by weight, and even more preferably 0.05 to 0.2 parts by weight. If the addition amount is less than the above lower limit value, the effect of the catalyst may be small and the reaction time may be significantly lengthened. If the addition amount exceeds the above upper limit value, the catalyst effect becomes excessive and a large amount of reaction heat is generated and the temperature. It can be difficult to control. The entire amount of the catalyst may be added at the start of the reaction, or may be added to the reaction system sequentially or divided as needed. Such sequential or divided catalyst injection suppresses the generation of a large amount of heat of reaction at the initial stage of the reaction, which makes it easier to control the reaction temperature.

The reaction temperature is not particularly limited, but is preferably 0 to 120 ° C, more preferably 20 to 100 ° C, and even more preferably 40 to 80 ° C. If the reaction is carried out at a temperature lower than the above lower limit, the reaction rate is extremely lowered, so that it takes a very long time to complete the reaction, and in some cases, the reaction may not be completed. On the other hand, if the reaction is carried out at a temperature exceeding the above upper limit value, impurities may be generated by a side reaction. Such impurities may cause coloration of the produced polyfunctional monomer for dental materials.

The reaction temperature is preferably controlled from the viewpoint of stable production in the above-mentioned preferable temperature range. Since the urethanization reaction is usually an exothermic reaction, cooling may be performed when the calorific value is large and the temperature of the reactant may rise beyond a preferable reaction temperature range. Further, when the reaction is almost completed and the temperature of the reaction product may drop beyond the preferable reaction temperature range, heating may be performed.

The polyfunctional monomer for dental materials of the present invention has polymerization activity. Therefore, during its production, unintended polymerization reactions may proceed when exposed to high temperatures. In order to prevent such an unintended polymerization reaction, a known polymerization inhibitor can be added before or during the reaction. The polymerization inhibitor is not particularly limited as long as it can suppress unintended polymerization of the (meth) acryloyl group in the production of the polyfunctional monomer for dental materials of the present invention. For example, dibutylhydroxytoluene (BHT) and hydroquinone (HQ) are used. , Hydroquinone monomethyl ether (MEHQ), phenothiazine (PTZ) and the like. Among these polymerization inhibitors, BHT is less consumed by reacting with isocyanate groups than other phenolic polymerization inhibitors, and is less colored as seen in amine-based polymerization inhibitors. Is particularly preferable. The amount of the polymerization inhibitor to be added is not particularly limited, but is based on 100 parts by weight of the total weight of the compound represented by the general formula (1A) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). , 0.001 to 0.5 parts by weight, more preferably 0.002 to 0.3 parts by weight, and even more preferably 0.005 to 0.3 parts by weight. , 0.005 to 0.1 parts by weight is more preferable, and 0.01 to 0.1 parts by weight is further preferable. If the addition amount is less than the above lower limit value, the ability as a polymerization inhibitor may not be exhibited, and if the addition amount exceeds the above upper limit value, it is cured when used as a dental material which is an application of a polyfunctional monomer for dental materials. The speed may be extremely slow, limiting its practicality.

A solvent may be used during the urethanization reaction. The solvent has no practical reactivity with the compound represented by the general formula (1A) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3), does not inhibit the reaction, and is a raw material and a product. It is not particularly limited as long as it dissolves a substance. Further, the reaction may be carried out without using a solvent. Since the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is usually a low-viscosity liquid, it can be miscible with the compound represented by the general formula (1A) without using a solvent. Can react to.

The method for mixing the compound represented by the general formula (1A) with the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is not particularly limited. For example, a method of adding and mixing the compound represented by the general formula (1A) in the reaction vessel while controlling the input amount of the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). A method of adding and mixing the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) in the reaction vessel while controlling the input amount of the compound represented by the general formula (1A). A method of simultaneously adding and mixing the compound represented by the general formula (1A) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) to the reaction vessel while controlling the input amount. There is. According to such a mixing method, the amount of heat generated by the urethanization reaction can be controlled within an appropriate range, so that the temperature control during the reaction becomes easy. Further, the urethanization reaction is carried out by putting the compound represented by the general formula (1A) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) in a total amount in a reaction vessel and then raising the temperature. The method can also be adopted. During the reaction, the reaction temperature may rise sharply due to the heat of reaction, so it may be necessary to control the temperature by cooling as appropriate.

Oxygen is effective as a polymerization inhibitor for compounds containing (meth) acryloyl groups. Therefore, during the reaction, oxygen may be introduced into the reactor to prevent unintended (meth) acryloyl group polymerization. Oxygen can be introduced into the reactor in the form of, for example, dry air or oxygen gas, but is preferably introduced into the reactor in the form of dry air. Dry air can be obtained by removing water by drying by a known method such as using a condensing air dryer or the like. As another embodiment, a mixed gas of an inert gas such as nitrogen and oxygen can be introduced into the reactor. The mode of the mixed gas of the inert gas such as nitrogen and oxygen is also preferable as in the mode of the dry air. The mixed gas of an inert gas such as nitrogen and oxygen can be obtained by mixing oxygen gas or the above-mentioned dry air containing oxygen with nitrogen at a predetermined ratio. The nitrogen is preferably dried by a known method to remove water. The introduction method is not particularly limited, but for example, it can be introduced continuously or intermittently in the form of bubbles from the bottom of the reaction vessel. Further, it may be introduced continuously or intermittently into the void portion in the upper part of the reaction vessel.

If water is present as an impurity in the system during the urethanization reaction, the (meth) acryloyl group-containing isocyanate compound represented by the above general formula (3) may react with water to generate an unintended impurity. Therefore, it is preferable that water does not exist in the reaction system as much as possible during the urethanization reaction.

Therefore, the water content of the compound represented by the general formula (1A) is preferably as small as possible, and specifically, the water content is 0.5 with respect to the compound represented by the general formula (1A). It is preferably 0% by weight or less, more preferably 0.3% by weight or less, and further preferably 0.1% by weight or less. When the amount of water contained in the compound represented by the general formula (1A) exceeds the above value, it is preferable to remove the water by a known method and then use it as a raw material for the polyfunctional monomer for dental materials of the present invention. .. Further, it is preferable that the inside of the reaction vessel where the urethanization reaction is carried out is dried by a known method to remove water.

[Monomer composition for dental materials containing a polyfunctional monomer for dental materials]
The polyfunctional monomer for dental materials according to the first aspect of the present invention can be used as a monomer composition for dental materials by blending other components, for example, components other than the polyfunctional monomer suitable for dental materials. .. This monomer composition for dental materials may be, for example, a polymerizable monomer other than the polyfunctional monomer for dental materials according to the first aspect of the present invention, which can be blended in the dental material described later (for example, other than the polyfunctional monomer of the present invention). (Meta) acrylate group-containing monomer) may be contained.

In the dental material monomer composition according to the first aspect of the present invention, for example, the content of the dental material polyfunctional monomer according to the first aspect of the present invention is 1.0 mass by mass with respect to the entire dental material monomer composition. % Or more (10% by mass or more, 50% by mass or more, 80% by mass or more, 90% by mass or more, etc.), 100% by mass or less (99% by mass or less, 90% by mass or less, 80% by mass or less, 50% mass or more) Hereinafter, it may be 10% by mass or less).

(Return mutation test)
It is desirable that the monomer composition for dental materials according to the first aspect of the present invention shows a negative result in the reverse mutation test. The reversion mutagenicity test (Ames test) means a test for examining the mutagenicity of a composition using a microorganism. The reversion mutation test in the present invention is carried out by the following method.

Specifically, the procedure is as follows under a fluorescent lamp with an ultraviolet absorbing film and / or an LED.
First, in a sterilized test tube, 0.1 mL of a test composition solution using dimethyl sulfoxide (DMSO) as a medium and 0.1 M phosphate buffer solution (pH 7.4) if metabolic activation is not activated are metabolically activated. In this case, 0.5 mL of S9mix, which will be described later, is added, and then 0.1 mL of the bacterial suspension, which will be described later, is added and mixed. After preincubating at 37 ° C. and about 100 rpm for 20 minutes, 2 mL of top agar described later is added and mixed, and the mixture is layered on a minimum glucose agar plate medium (5 doses or more) described later. After confirming the stratified solidification, the minimum glucose agar plate medium is turned upside down and cultured at 37 ° C. for 48 hours. Negative / positive judgment is made on the cultured plate. When testing a negative control substance, DMSO is used as the negative control substance, and 0.1 mL of the medium is added instead of the test composition solution in the above step.

After the culture is completed, the number of reverted mutant colonies on each plate is counted.
With respect to the negative / positive criteria, the test composition was used in all strains and at all doses, and in both non-metabolic and metabolically activated cases, compared to the case of only the negative control substance. If the average number of colonies is within 2 times, the composition is judged to be negative.

In the reversion mutation test, the maximum dose of the test substance (specifically, the polyfunctional monomer for dental materials contained in the monomer composition for dental materials) contained in the test composition solution is 5000 μg / plate, and the following Prepare to a dose of 5 or more divided by a common ratio of 2-4.

As the strain, Salmonella enterica TA100, TA1535, Escherichia coli WP2uvrA, which is a base pair substitution mutant, or Salmonella enterica TA98, or TA1537, which is a frameshift mutant, is used.

As the minimum glucose agar plate medium, Testmedia AN medium (manufactured by Oriental Yeast Co., Ltd., for mutagenicity test) is used.
The minimum glucose agar plate medium per dose should be 2 or more for negative control substances and 2 or more for test compositions.

The case of metabolically activating means the case of adding S9mix (a rat liver microsome fraction to which a coenzyme is added) together with the test substance, and the case of not metabolically activating means the case of not adding S9mix. To do. Specifically, the composition of S9mix is S9 (supernatant portion when liver homogenate is centrifuged at 9000 × g): 0.1 mL, MgCl2: 8 μmol, KCl: 33 μmol, glucose-6-phosphate: 5 μmol. , NADPH: 4 μmol, NAPH: 4 μmol, sodium phosphate buffer (pH 7.4): 100 μmol.

For top agar, the amino acid solution (0.5 mmol / L L-histidine, 0.5 mmol / L D-biotin, 0.5 mmol / L L-tryptophane) was sterilized by filtration, while the soft agar solution (0.6% (0.6% (0.6%)). w / v) agar (Bacto-Agar), 0.5% (w / v) sodium chloride) was sterilized by high pressure steam at 121 ° C. for 20 minutes, and the soft agar solution dissolved in the amino acid solution was sterilized in a volume ratio of 1:10. Use the mixture in.
For the preparation of the bacterial suspension for each cell, cell concentration (1 × 10 ⁹ bacteria count / mL or higher) and use those prepared. A nutrient broth culture solution is used for culturing each cell. Nutrient broth culture medium was prepared for Nutrient broth No. 2 (Oxoid, Nutrient Bouillon No. 2) is dissolved in purified water to a concentration of 2.5 wt%, and high-pressure steam sterilization is performed at 121 ° C. for 20 minutes to prepare.

(Cytotoxicity test by NRU method)
The monomer composition for dental materials according to the first aspect of the present invention may have a relative cell viability within a certain range in a cytotoxicity test by the NRU method using Balb / 3T3 cells described later. The cytotoxicity test is performed by the following method.

In Balb / 3T3 cells (Balb / 3T3 clone A31 cells (mouse skin-derived fibroblasts)) seeded in 96-well plates at 10000 cells / well and pre-cultured for 25 hours, the medium of each well was removed, and the test composition was prepared. Add 0.1 mL of the containing test solution or negative control solution and _{incubate in a CO 2} incubator for 24 hours. At this time, 12 wells are used for the negative control solution and 6 wells are used for the test solution. After culturing, observe each well under a microscope to confirm cell growth, remove the culture solution from each well, and wash with 0.15 mL of PBS. After washing, 0.1 mL of the NR culture solution is added, and the _{cells are cultured in a CO 2} incubator for 3 hours for staining. After culturing, the culture solution in each well is removed and washed with 0.15 mL of PBS. Add 0.15 ml of NR redissolve to each well and shake with a plate shaker for 10 minutes. Neutral red (NR) is dissolved in the NR redissolved solution, and the absorbance of the solution in each well after dissolution at 540 nm is measured, and the average value is obtained. When the absorbance of the solution in the well to which the negative control solution was added was set to 100, the absorbance of the solution in the well to which the test solution was added was set to the absorbance of the solution in the well to which the test solution was added. The relative cell viability (%) of the (monomer composition for dental materials).

To prepare a test solution containing the test composition, first add the test composition to DMSO and then dilute with DMSO to prepare a DMSO solution. Then, 10 μL of the above-mentioned DMSO solution is added per 2 mL of the D05 culture solution described later, and the mixture is stirred and mixed to prepare a test solution. The test solution is adjusted so that the test substance contained in the test composition solution (specifically, the polyfunctional monomer for dental materials contained in the monomer composition for dental materials) has a predetermined concentration.
The negative control solution is prepared by adding DMSO to the D05 culture solution at 0.5 v / v%.

The D05 culture medium is D-MEM (Dulvecco's Modified Eagle's Medium 9, Cat No. 048-30275) containing 5 vol% of calf serum, 1 mmol / L sodium pyruvate, and 1 vol% of penicillin-streptomycin-amphotericin B suspension. , Glutamine 584 mg / L and HEPES 5.958 g / L).
The D10 culture medium refers to D-MEM containing 10 vol% of calf serum, 1 vol% of penicillin-streptomycin-amphotericin B suspension, and 1 vol% of 100 mmol / L sodium pyruvate solution.
In the above-mentioned preculture of Balb / 3T3 cells, cells in the logarithmic growth phase are first isolated using trypsin-EDTA, and then ^{a cell suspension having a cell concentration of 1x10 5} cells / mL is prepared using a D05 culture medium. Then, 0.1 mL of the cell suspension is dispensed and seeded on a 96-well plate (1x10 ⁴ cells / well), and allowed to stand in a _{CO 2 incubator for 25 hours.}

The NR culture solution refers to a solution in which an NR (neutral red) stock solution and a D10 culture solution are mixed at a ratio of 1:79, left at 37 ° C. overnight, and then filtered through a filter to remove NR crystals.
The NR (neutral red) stock solution refers to a 0.4% (w / v) aqueous solution of neutral red (NR) (manufactured by Wako Pure Chemical Industries, Ltd.).
The NR redissolved solution refers to a mixture of acetic acid, ethanol and water at a ratio of 1:50:49. Prepare within 1 hour before use.

For example, the concentration of the test substance contained in the test composition in the test solution is, for example, 0.00164 mg / mL, 0.00410 mg / mL, 0.0102 mg / mL, 0.0256 mg / mL, 0.0640 mg / mL, It may be 0.160 mg / mL, 0.400 mg / mL, or 1.00 mg / mL.

The concentrations of the test substance contained in the test composition in the test solution are 0.00164 mg / mL, 0.00410 mg / mL, 0.0102 mg / mL, 0.0256 mg / mL, 0.0640 mg / mL, 0.160 mg / mL. , 0.400 mg / mL or 1.00 mg / mL, the relative cell viability by the NRU method using the above-mentioned BALB / 3T3 cells is 0.01% or more (0.05% or more, 0.1% or more). , 0.5% or more, 1.0% or more, 5.0% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more , 90% or more, 95% or more, 99% or more, etc.), 100% or less (99% or less, 95% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less , 40% or less, 30% or less, 20% or less, 10% or less, 5.0% or less, 1.0% or less, 0.5% or less, 0.1% or less, 0.05% or less, etc.) You may.

(Cell test by WST method)
The monomer composition for dental materials according to the first aspect of the present invention may have a relative cell growth rate within a certain range in a cell test by the WST method using Balb / 3T3 cells. The cell test is performed by the following method.

For Balb / 3T3 cells (Balb / 3T3 clone A31 cells (mouse skin-derived fibroblasts)) seeded in a 96-well plate at 2000 cells / well and pre-cultured for 24 hours, the culture solution in each well was removed, and the test composition was prepared. Add 0.1 mL of test solution or negative control solution containing _{, and incubate in a CO 2} incubator for 48 hours. At this time, 6 wells are used for the negative control solution, and 3 wells are used for the test solution.

After culturing, discard the test solution or negative control solution, wash with PBS, add 0.2 mL of DMEM culture solution containing 10% WST-8 reagent to each well, and perform a color reaction _{in a CO 2 incubator for 2 hours.} .. For the liquid in the wells after the reaction, the absorbance at 450 nm and 650 nm was measured with a microplate reader, and the value obtained by subtracting the absorbance at 650 nm from the absorbance of the liquid in each well at 450 nm was defined as the absorbance in each well, and the value became negative. If so, the average value of the absorbance is calculated as 0. The value obtained by dividing the average absorbance of the solution in the well to which the test solution was added by the average absorbance of the solution in the well to which the negative control solution was added is the value obtained by dividing the value by the average absorbance of the solution in the well to which the test solution was added. The relative cell growth rate (%) of the material monomer composition).

To prepare a test solution containing the test composition, first add the test composition to DMSO and then dilute with DMSO to prepare a DMSO solution. Then, 5 μL of DMSO diluted solution is added per 1 mL of DMEM culture solution to prepare a test solution. The test solution is adjusted so that the test substance contained in the test composition solution (specifically, the polyfunctional monomer for dental materials contained in the monomer composition for dental materials) has a predetermined concentration.
Negative control solution is prepared by adding DMSO to DMEM culture medium at a concentration of 0.5 vol%.
DMEM culture medium refers to Dulvecco's Modified Eagle's Medium (D-MEM) containing 10 vol% calf serum and 1 vol% penicillin-streptomycin-amphotericin B suspension (x100).
In the above-mentioned preculture of Balb / 3T3 cells, first, Balb / 3T3 clone A31 cells in the logarithmic growth phase are isolated using 0.25% trypsin-1 mM EDTA, and then the cell concentration is 20000 cells / using a DMEM culture medium. After preparing mL of cell suspension, 0.1 mL of cell suspension is dispensed and seeded on a 96-well plate (2000 cells / well) and allowed to stand in a _{CO 2 incubator for 24 hours.}

For example, the concentration of the test substance contained in the test composition in the test solution is, for example, 0.00164 mg / mL, 0.00410 mg / mL, 0.0102 mg / mL, 0.0256 mg / mL, 0.0640 mg / mL, It may be 0.160 mg / mL, 0.400 mg / mL, or 1.00 mg / mL.

The concentrations of the test substance contained in the test composition in the test solution are 0.00164 mg / mL, 0.00410 mg / mL, 0.0102 mg / mL, 0.0256 mg / mL, 0.0640 mg / mL, 0.160 mg / mL. , 0.400 mg / mL or 1.00 mg / mL, the relative cell growth inhibition rate by the WST method using the above-mentioned BALB / 3T3 cells is 0.001% or more (0.01% or more, 0.05%). 0.1% or more, 0.5% or more, 1.0% or more, 5.0% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, It may be 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, etc., and may be 100% or less (99% or less, 95% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5.0% or less, 1.0% or less, 0.5% or less, 0.1% or less, 0. 05% or less, 0.01% or less, etc.) may be used.

[Dental material containing polyfunctional monomer for dental material]
The polyfunctional monomer for dental materials according to the first aspect of the present invention is suitable as a raw material for dental materials. In contrast to the polyfunctional monomer for dental materials of the present invention, a component other than the polyfunctional monomer for dental materials of the present invention (for example, a polymerizable monomer other than the polyfunctional monomer for dental materials (other than the polyfunctional monomer of the present invention) By blending (meth) an acrylate group-containing monomer, an epoxy group-containing monomer, etc.), a dental material containing the polyfunctional monomer for dental materials of the present invention can be produced.

[Monomer containing (meth) acrylate group other than the polyfunctional monomer of the present invention]
As an example of a component other than the polyfunctional monomer for dental materials according to the first aspect of the present invention, a (meth) acrylate group-containing monomer other than the polyfunctional monomer of the present invention can be mentioned.

The (meth) acrylate group-containing monomer other than the above-mentioned polyfunctional monomer of the present invention contains one or more (meth) acrylate groups in the molecule. The number of polymerizable groups contained may be one or two or more.

The (meth) acrylate group-containing monomer other than the above-mentioned polyfunctional monomer of the present invention may be composed of one kind of compound or a mixture of two or more kinds of compounds.
Examples of the (meth) acrylate group-containing monomer other than the above-mentioned polyfunctional monomer having only one polymerizable group include a monomer represented by the following general formula (21).

上記一般式（２１）中、Ｒ^21aは水素またはメチル基であり、Ｒ^21bは酸素または窒素を含有してもよい炭素数１〜２０の一価の有機基を示す。

In the general formula (21), R ^21a is a hydrogen or methyl group, and R ^21b is a monovalent organic group having 1 to 20 carbon atoms which may contain oxygen or nitrogen.

Examples of the monovalent organic group include acyclic hydrocarbon groups having 1 to 20 carbon atoms such as an alkyl group, an alkenyl group and an alkynyl group, and carbons such as a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group and an aryl group. Hydrocarbon groups such as cyclic hydrocarbon groups of number 1 to 20; oxygen is inserted between carbon-carbon bonds of at least a part of the above hydrocarbon groups such as alkoxyalkyl groups, alkoxyalkylene glycol groups and tetrahydrofurfuryl groups. Examples thereof include oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms such as the groups (however, oxygen is not continuously inserted). The cyclic hydrocarbon group having 1 to 20 carbon atoms may have an acyclic hydrocarbon moiety. Further, the acyclic hydrocarbon moiety contained in these groups may be either linear or branched.

When the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms contains a linear alkylene portion, at least one methylene group thereof is an ester bond or an amide. It may be replaced with a bond, carbonate bond, urethane bond (carbamoyl group), or urea bond (however, the methylene group is not continuously replaced).

Further, the hydrogen atom contained in the organic group such as the hydrocarbon group having 1 to 20 carbon atoms and the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms is an acid group such as a carboxyl group or a phosphoric acid group, a hydroxyl group or an amino group. , It may be replaced with a functional group such as an epoxy group.

Examples of the compound having a methacryloyl group represented by the above general formula (21) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, ethoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate and phenoxyethyl. Examples thereof include methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 4-hydroxybutyl methacrylate, and 1,4-cyclohexanedimethanol monomethacrylate.

Examples of the compound having an acryloyl group represented by the general formula (21) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, and phenoxyethyl. Examples thereof include acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate.

Examples of the (meth) acrylate group-containing monomer other than the polyfunctional monomer of the present invention having two or more polymerizable groups include a monomer represented by the following general formula (22).

上記一般式（２２）中、Ｒ^22aおよびＲ^22bは水素またはメチル基を示し、これらは同一でも異なっていてもよく、Ｒ^22cは酸素または窒素を含有してもよい炭素数１〜４０の二価の有機基を示す。

In the above general formula (22), R ^22a and R ^22b represent hydrogen or methyl groups, which may be the same or different, and R ^22c may contain oxygen or nitrogen and has 1 to 40 carbon atoms. Indicates a valent organic group.

Examples of the divalent organic group include an acyclic hydrocarbon group having 1 to 40 carbon atoms such as an alkylene group, an alkenylene group and an alkynylene group, a cycloalkylene group, a cycloalkenylene group, a cycloalkynylene group and an arylene group. A hydrocarbon group such as a cyclic hydrocarbon group having 1 to 40 carbon atoms; a group in which oxygen is inserted between carbon-carbon bonds of at least a part of the above-mentioned hydrocarbon group such as an oxyalkylene group (however, oxygen is continuous). An oxygen-containing hydrocarbon group having 1 to 40 carbon atoms such as (is not inserted) can be mentioned. The cyclic hydrocarbon group having 1 to 40 carbon atoms may have an acyclic hydrocarbon moiety. Further, the acyclic hydrocarbon moiety contained in these groups may be either linear or branched.

When the above-mentioned hydrocarbon group having 1 to 40 carbon atoms or the oxygen-containing hydrocarbon group having 1 to 40 carbon atoms contains a linear alkylene portion, at least one methylene group thereof is an ester bond or an amide. It may be replaced with a bond, carbonate bond, urethane bond (carbamoyl group), or urea bond (however, the methylene group is not continuously replaced).

Further, the hydrogen atom contained in the organic group such as the above-mentioned hydrocarbon group having 1 to 40 carbon atoms and the oxygen-containing hydrocarbon group having 1 to 40 carbon atoms is an acid group such as a carboxyl group or a phosphoric acid group, a hydroxyl group or an amino group. , A functional group such as an epoxy group, or a polymerizable group such as an acryloyl group or a methacryloyl group may be substituted.

Among the monomers represented by the general formula (22), an example of a suitable monomer is a monomer in which R ^22c is a linear alkylene group having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms.

Examples of the above-mentioned suitable monomer and compound having a methacryloyl group include 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,8-octanediol dimethacrylate, and 1,9-nonanediol. Examples thereof include dimethacrylate and 1,10-decanediol dimethacrylate.

Examples of the above-mentioned suitable monomer and compound having an acryloyl group include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate, and 1,9-nonanediol. Examples thereof include diacrylate and 1,10-decanediol diacrylate.

Further, among the monomers represented by the general formula (22), as another example of a suitable monomer, R ^22C is a linear oxyalkylene group having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms. Monomers can be mentioned.

Examples of the above-mentioned suitable monomer and compound having a methacryloyl group include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and tetra. Examples thereof include propylene glycol dimethacrylate and polypropylene glycol dimethacrylate.

Examples of the above-mentioned suitable monomer and compound having an acryloyl group include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate and tetra. Examples thereof include propylene glycol diacrylate and polypropylene glycol diacrylate.

Further, among the monomers represented by the general formula (22), as another example of a suitable monomer, a monomer having a carbamoyl group represented by the following general formula (23) can be mentioned.

上記一般式（２３）中、Ｒ^23aおよびＲ^23bは水素またはメチル基であり、これらは同一でも異なっていてもよく、Ｒ^23cおよびＲ^23dは酸素を含有してもよい炭素数１〜１２の二価の有機基であり、これらは同一でも異なっていてもよい。

In the above general formula (23), R ^23a and R ^23b are hydrogen or methyl groups, which may be the same or different, and R ^23c and R ^23d may contain oxygen and have 1 to 12 carbon atoms. It is a divalent organic group, which may be the same or different.

Examples of the divalent organic group include an acyclic hydrocarbon group having 1 to 12 carbon atoms such as an alkylene group, and a hydrocarbon group such as a cycloalkylene group and an arylene group having 1 to 12 carbon atoms. The carbon number 1 to 1 of a group in which oxygen is inserted (however, oxygen is not continuously inserted) between carbon-carbon bonds of at least a part of the above hydrocarbon group such as an oxyalkylene group. Twelve oxygen-containing hydrocarbon groups and the like can be mentioned. The cyclic hydrocarbon group having 1 to 12 carbon atoms may have an acyclic hydrocarbon moiety. Further, the acyclic hydrocarbon moiety contained in these groups may be either linear or branched.

Further, the hydrogen atom contained in the organic group such as the hydrocarbon group having 1 to 12 carbon atoms and the oxygen-containing hydrocarbon group having 1 to 12 carbon atoms is an acid group such as a carboxyl group or a phosphoric acid group, a hydroxyl group or an amino group. , A functional group such as an epoxy group, or a polymerizable group such as an acryloyl group or a methacryloyl group may be substituted.

In the above general formula (23), R ^23e represents a divalent organic group having 1 to 20 carbon atoms which may contain oxygen.
Examples of the divalent organic group include an acyclic hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, and a hydrocarbon group such as a cycloalkylene group and an arylene group having 1 to 20 carbon atoms. The carbon number 1 to 1 of a group in which oxygen is inserted (however, oxygen is not continuously inserted) between carbon-carbon bonds of at least a part of the above hydrocarbon group such as an oxyalkylene group. 20 oxygen-containing hydrocarbon groups and the like can be mentioned. The cyclic hydrocarbon group having 1 to 20 carbon atoms may have an acyclic hydrocarbon moiety. Further, the acyclic hydrocarbon moiety contained in these groups may be either linear or branched.

Further, the hydrogen atom contained in the organic group such as the hydrocarbon group having 1 to 20 carbon atoms or the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms is an acid group such as a carboxyl group or a phosphoric acid group, a hydroxyl group or an amino group. , It may be replaced with a functional group such as an epoxy group.

Examples of the compound having an acryloyl group represented by the general formula (23) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxy. Hydroxy acrylates such as butyl acrylate or 1,4-cyclohexanedimethanol monoacrylate and 2,4- or 2,6-toluene diisocyanate, 4,4'-, 2,4'-or 2,2'-diphenylmethane- Examples thereof include urethane acrylate which is a reaction product with diisocyanate such as diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene-diisocyanate. Examples of such urethane acrylates include 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) diacrylate.

As another suitable example of the compound having a (meth) acryloyl group represented by the general formula (23), at least one selected from the group consisting of the compounds represented by the following general formulas (24a) to (24e) is selected. One can be mentioned.

また、好ましい上記一般式（２２）で示されるモノマーの別の例として、下記一般式（２５）のモノマーを挙げることができる。

Further, as another example of the preferable monomer represented by the general formula (22), the monomer of the following general formula (25) can be mentioned.

In the above general formula (25), R ^25a and R ^25b represent hydrogen or methyl groups, which may be the same or different, and R ^25c and R ^25d may contain oxygen and have 1 to 12 carbon atoms. It represents divalent organic groups, which may be the same or different. Examples of the divalent organic group include an acyclic hydrocarbon group having 1 to 12 carbon atoms such as an alkylene group, and a hydrocarbon group such as a cycloalkylene group and an arylene group having 1 to 12 carbon atoms. The carbon number 1 to 1 of a group in which oxygen is inserted (however, oxygen is not continuously inserted) between carbon-carbon bonds of at least a part of the above hydrocarbon group such as an oxyalkylene group. Twelve oxygen-containing hydrocarbon groups and the like can be mentioned. The cyclic hydrocarbon group having 1 to 12 carbon atoms may have an acyclic hydrocarbon moiety. Further, the acyclic hydrocarbon moiety contained in these groups may be either linear or branched. Further, the hydrogen atom contained in the organic group such as the hydrocarbon group having 1 to 12 carbon atoms and the oxygen-containing hydrocarbon group having 1 to 12 carbon atoms is an acid group such as a carboxyl group or a phosphoric acid group, a hydroxyl group or an amino group. , A functional group such as an epoxy group, or a polymerizable group such as an acryloyl group or a methacryloyl group may be substituted.

In the above general formula (25), R ^25e represents a divalent organic group having 1 to 20 carbon atoms which may contain oxygen. Examples of the divalent organic group include a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a cycloalkylene group and an arylene group; and a carbon-carbon bond of at least a part of the hydrocarbon group such as an oxyalkylene group. Examples thereof include an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms such as a group into which oxygen is inserted (however, oxygen is not continuously inserted). The cyclic hydrocarbon group having 1 to 20 carbon atoms may have an acyclic hydrocarbon moiety. Further, the hydrogen atom contained in the organic group such as the hydrocarbon group having 1 to 20 carbon atoms and the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms is an acid group such as a carboxyl group or a phosphoric acid group, a hydroxyl group or an amino group. , It may be replaced with a functional group such as an epoxy group.

Examples of the compound having a methacryloyl group represented by the above general formula (25) include 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GMA) and ethylene oxide modification. Examples thereof include bisphenol A dimethacrylate and propylene oxide-modified bisphenol A dimethacrylate.

Examples of the compound having an acryloyl group represented by the general formula (25) include 2,2-bis [4- (3-acryloyloxy-2-hydroxypropoxy) phenyl] propane, ethylene oxide-modified bisphenol A diacrylate, and the like. Examples thereof include propylene oxide-modified bisphenol A diacrylate.

Further, when a dental material containing the polyfunctional monomer for dental materials of the present invention is used for the purpose of a dental adhesive, it can be adhered as a (meth) acrylate group-containing monomer other than the polyfunctional monomer of the present invention. It is preferable that a monomer that exerts a function is contained. Examples of the (meth) acrylate group-containing monomer other than the polyfunctional monomer of the present invention exhibiting such an adhesive function include a monomer having at least one polymerizable group and an acidic group selected from a methacryloyl group and an acryloyl group. Be done. Examples of the acidic group include a phosphoric acid residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, a sulfonic acid residue and the like.

Examples of the monomer having a methacryloyl group and a phosphoric acid residue include 2-methacryloyloxyethyl dihydrogen phosphate, 9-methacryloyloxynonyl dihydrogen phosphate, 10-methacryloyloxydecyldihydrogen phosphate, and 11-methacryloyloxy. Undecyldihydrogen phosphate, 20-methacryloyloxyeicosil dihydrogen phosphate, 1,3-dimethacryloyloxypropyl-2-dihydrogen phosphate, 2-methacryloyloxyethylphenyl phosphate, 2-methacryloyloxyethyl 2' -Bromoethyl phosphoric acid, methacryloyloxyethyl phenylphosphonate, and acidified products thereof.

Examples of the monomer having an acryloyl group and a phosphate residue include 2-acryloyloxyethyl dihydrogen phosphate, 9-acryloyloxynonyl dihydrogen phosphate, 10-acryloyloxydecyldihydrogen phosphate, and 11-acryloyloxy. Undecyldihydrogenphosphate, 20-acryloyloxyeicosildihydrogenphosphate, 1,3-diacryloyloxypropyl-2-dihydrogenphosphate, 2-acryloyloxyethylphenyl phosphate, 2-acryloyloxyethyl 2' -Bromoethyl phosphate, acryloyloxyethylphenylphosphonate, and acidified products thereof.

Examples of the monomer having a methacryloyl group and a pyrophosphate residue include di (2-methacryloyloxyethyl) pyrophosphate and acid chlorides thereof.
Examples of the monomer having an acryloyl group and a pyrophosphate residue include di (2-acryloyloxyethyl) pyrophosphate and acid chlorides thereof.

Examples of the monomer having a methacryloyl group and a thiophosphate residue include 2-methacryloyloxyethyl dihydrogendithiophosphate, 10-methacryloyloxydecyldihydrogenthiophosphate, and acid chlorides thereof.

Examples of the monomer having an acryloyl group and a thiophosphate residue include 2-acryloyloxyethyl dihydrogendithiophosphate, 10-acryloyloxydecyldihydrogenthiophosphate, and acid chlorides thereof.

Examples of the monomer having a methacryloyl group and a carboxylic acid residue include 4-methacryloyloxyethoxycarbonylphthalic acid, 5-methacryloylaminopentylcarboxylic acid, 11-methacryloyloxy-1,1-undecandicarboxylic acid, and these acids. Examples include chlorides and acid anhydrides.

Examples of the monomer having an acryloyl group and a carboxylic acid residue include 4-acryloyloxyethoxycarbonylphthalic acid, 5-acryloylaminopentylcarboxylic acid, 11-acryloyloxy-1,1-undecandicarboxylic acid, and these acids. Examples thereof include chlorides and acid anhydrides.

Examples of the monomer having a methacryloyl group and a sulfonic acid residue include 2-sulfoethyl methacrylate and 2-methacrylamide-2-methylpropanesulfonic acid.

Examples of the monomer having an acryloyl group and a sulfonic acid residue include 2-sulfoethyl acrylate and 2-acrylamide-2-methylpropane sulfonic acid.

[Polymerization initiator]
As another example of the components other than the polyfunctional monomer for dental materials of the present invention contained in the dental material of the first aspect of the present invention, a polymerization initiator can be mentioned.

As the polymerization initiator, a general polymerization initiator used in the dental field can be used, and it is usually selected in consideration of the polymerizable property of the polymerizable monomer and the polymerization conditions.
When performing normal temperature polymerization, for example, a redox-based polymerization initiator in which an oxidizing agent and a reducing agent are combined is suitable. When a redox-based polymerization initiator is used, it is necessary to take the form in which the oxidizing agent and the reducing agent are separately packaged and mix them immediately before use.

The oxidizing agent is not particularly limited, and examples thereof include organic peroxides such as diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides and hydroperoxides. Can be done. Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-toluyl peroxide; t-butylperoxybenzoate and bis-t-butylperoxy. Peroxyesters such as isophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-2-ethylhexanoate and t-butylperoxyisopropylcarbonate; dicumyl Dialkyl peroxides such as peroxides, di-t-butyl peroxides and lauroyl peroxides; peroxyketals such as 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane; methylethylketones Ketone peroxides such as peroxide; hydroperoxides such as t-butyl hydroperoxide and the like can be mentioned.

The reducing agent is not particularly limited, but a tertiary amine is usually used. Examples of the tertiary amine include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-. Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-i-propylaniline, N, N- Dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-) Hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N -Bis (2-hydroxyethyl) -4-i-propylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-di (2-hydroxyethyl) -3,5 -Di-i-propylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, ethyl 4-dimethylaminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate, 4-Dimethylaminobenzoic acid (2-methacryloyloxy) ethyl, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino) Ethyl methacrylate, N, N-bis (methacryloyloxyethyl) -N-methylamine, N, N-bis (methacryloyloxyethyl) -N-ethylamine, N, N-bis (2-hydroxyethyl) -N-methacryloyloxy Examples thereof include ethylamine, N, N-bis (methacryloyloxyethyl) -N- (2-hydroxyethyl) amine, tris (methacryloyloxyethyl) amine and the like.

In addition to these organic peroxide / amine systems ^{, redox systems such as cumenehydroperoxide / thiourea system, ascorbic acid / Cu 2+} salt system, and organic peroxide / amine / sulfinic acid (or salt thereof) system. A polymerization initiator can be used. Further, as the polymerization initiator, tributylborane, organic sulfinic acid and the like are also preferably used.

When performing thermal polymerization by heating, it is preferable to use a peroxide or an azo compound.
The peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like. The azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile.

When photopolymerization by irradiation with visible light is performed, redox-based initiators such as α-diketone / tertiary amine, α-diketone / aldehyde, and α-diketone / mercaptan are preferable.
The photopolymerization initiator is not particularly limited, and examples thereof include α-diketone / reducing agent, ketal / reducing agent, and thioxanthone / reducing agent. Examples of the α-diketone include camphorquinone, benzyl and 2,3-pentanedione. Examples of the ketal include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of the thioxanthone include 2-chlorothioxanthone and 2,4-diethylthioxanthone. Examples of the reducing agent include Mihira-ketone, 2- (dimethylamino) ethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, N, N-dimethylaminobenzoate ethyl, and the like. Butyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone, N, N-bis (2-hydroxyethyl) -p-toluidine, dimethylaminophenanthol, etc. Tertiary amines of And compounds having a thiol group such as thiobenzoic acid; and the like. An α-diketone / organic peroxide / reducing agent system in which an organic peroxide is added to these redox systems is also preferably used.

When photopolymerization by ultraviolet irradiation is performed, benzoin alkyl ether, benzyl dimethyl ketal and the like are suitable. Further, a photopolymerization initiator of (bis) acylphosphine oxides is also preferably used.

Among the (bis) acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenyl. Phosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide and benzoyldi- (2,6) -Dimethylphenyl) Phosphate and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis- ( 2,6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis -(2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4) Examples include 6-trimethylbenzoyl) phenylphosphine oxide and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide. The photopolymerization initiators of these (bis) acylphosphine oxides can be used alone or in combination with reducing agents such as various amines, aldehydes, mercaptans and sulfinates. These can also be suitably used in combination with the above-mentioned visible light photopolymerization initiator.

The polymerization initiator or photopolymerization initiator can be used alone or in combination of two or more, and the blending amount is usually 0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the dental material. It is used in the range of 0.1 to 5 parts by weight.

[Filler]
As another example of the components other than the polyfunctional monomer for dental materials of the present invention contained in the dental material of the first aspect of the present invention, a filler can be mentioned.

As the filler, a general filler used in the dental field can be used. Fillers are usually roughly classified into organic fillers and inorganic fillers.
Examples of the organic filler include polymethyl methacrylate, ethyl polymethacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, ethylene-vinyl acetate copolymer and the like. Examples thereof include fine powders such as a styrene-butadiene copolymer.

Examples of the inorganic filler include various glass types (mainly silicon dioxide and, if necessary, oxides such as heavy metal, boron and aluminum), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.). , Activated clay, synthetic zeolite, mica, calcium fluoride, itterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite and other fine powders. Among these inorganic fillers, those used as an X-ray contrast agent are preferable. Specific examples of the inorganic filler that can also be used as an X-ray contrast agent include barium borosilicate glass (Kimble Raysorb T3000, Shot 8235, Shot GM27884 and Shot GM39923), and strontium boroaluminosilicate glass (Raysorb T4000, Shot). G018-093 and Shot GM32087, etc.), Lantern glass (Shot GM31684, etc.), Fluoroaluminosilicate glass (Shot G018-091 and Shot G018-117, etc.), Zolconium and / or cesium-containing boroaluminosilicate glass (Shot G018-307, etc.) , G018-308 and G018-310, etc.).

Further, an organic-inorganic composite filler obtained by adding a polymerizable monomer to these inorganic fillers in advance to form a paste, curing the polymerization, and pulverizing the mixture may be used.
Further, a dental material containing a microfiller having a particle size of 0.1 μm or less is one of the suitable embodiments for a dental composite resin. As the material of the filler having such a small particle size, silica (for example, trade name Aerosil), alumina, zirconia, titania and the like are preferable. The formulation of such an inorganic filler having a small particle size is advantageous in obtaining the polishing smoothness of the cured product of the composite resin.

Depending on the purpose, these fillers may be surface-treated with a silane coupling agent or the like. Examples of such surface treatment agents include known silane coupling agents such as γ-methacryloxyalkyltrimethoxysilane (number of carbon atoms between methacryloxy group and silicon atom: 3 to 12) and γ-methacryloxyalkyltriethoxy. Organic silicon compounds such as silane (number of carbon atoms between methacryloxy group and silicon atom: 3-12), vinyltrimethoxysilane, vinylethoxysilane and vinyltriacetoxysilane are used. The concentration of the surface treatment agent is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the filler.

These fillers are appropriately used alone or in combination of two or more. The blending amount of the filler may be appropriately determined in consideration of the operability (viscosity) of the composite resin paste and the mechanical properties of the cured product thereof, and is 100 parts by weight of all the components other than the filler contained in the dental material. On the other hand, it is usually 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight, and more preferably 100 to 600 parts by weight.
Dental materials containing a monomer containing a (meth) acryloyl group, a polymerization initiator, and a filler as described above may be referred to as a composite resin.

[Other ingredients]
The dental material of the first aspect of the present invention is the above-mentioned polyfunctional monomer for dental material of the present invention, a polymerizable monomer other than the polyfunctional monomer of the present invention (for example, a (meth) acrylate other than the polyfunctional monomer of the present invention). Ingredients other than the group-containing monomer (monomer having an epoxy group), the polymerization initiator, and the filler may be appropriately contained depending on the intended purpose. For example, the above-mentioned polymerization inhibitor may be contained in order to improve storage stability. In addition, pigments such as known pigments and dyes may be included in order to adjust the color tone. Further, in order to improve the strength of the cured product, a known reinforcing material such as fiber may be included. It may also contain a solvent such as water, ethanol or acetone.

[Ratio of each component]
The amount of the polyfunctional monomer blended in the dental material according to the first aspect of the present invention is not particularly limited, but is, for example, in the range of 0.1 to 99%. The preferred blending amount may vary depending on the application for the dental material, and for example, a polymerizable monomer component (the above-mentioned polyfunctional monomer for dental material of the present invention and a polymerizable monomer other than the above-mentioned polyfunctional monomer of the present invention). (For example, a (meth) acrylate group-containing monomer other than the polyfunctional monomer of the present invention, a monomer having an epoxy group) is blended in an amount of 1 to 50% by weight, more preferably 3 to 30% by weight. When the application is a composite resin for filling, a hard resin for crown, a resin for artificial dentistry, or a resin block for CAD / CAM, the blending amount of the polyfunctional monomer is 1 to 50% by weight in the polymerizable monomer component. The content of the dental material is preferably 3 to 30% by weight. The use of the dental material is a dental adhesive material (orthodontic adhesive material, bonding material, adhesive resin cement, adhesive composite resin for filling, resin-added glass monomer). In the case of cement, etc.), a dental primer, and a tooth fissure sealing material, the blending amount of the polyfunctional monomer is preferably 1 to 50% by weight in the polymerizable monomer component, and is preferably 3 to 20% by weight. Is more preferable.

(Return mutation test)
The dental material of the polyfunctional monomer of the first aspect of the present invention may be negative in the reversion mutation test. In the method of the reversion mutation test (Ames test), the monomer composition for the dental material of the first aspect of the present invention is used in the above-mentioned method of the reversion mutation test, and the dental material of the polyfunctional monomer of the first aspect of the present invention is used. Replace with and follow the same procedure.

(Cell test by NRU method)
The dental material of the polyfunctional monomer of the first aspect of the present invention may have a relative cell viability within a certain range in a cell test by the NRU method using Balb / 3T3 cells. The cell test is carried out in the same procedure as the above-mentioned cell test by the NRU method, in which the monomer composition for dental material of the first aspect of the present invention is replaced with the dental material of the polyfunctional monomer of the first aspect of the present invention. .. Further, the concentration of the test substance (polyfunctional monomer for dental material contained in the dental material) contained in the test material in the test solution and the relative cell growth rate (%) of the dental material are determined by the above-mentioned first aspect of the present invention. It may be the same as in the case of the monomer composition for dental materials.

(Cell test by WST method)
The dental material of the polyfunctional monomer of the first aspect of the present invention may have a relative cell growth rate within a certain range in a cell test by the WST method using Balb / 3T3 cells. The cell test is carried out in the same procedure as in the cell test by the WST method described above, in which the monomer composition for dental material of the first aspect of the present invention is replaced with the dental material of the polyfunctional monomer of the first aspect of the present invention. .. Further, the concentration of the test substance (polyfunctional monomer for dental material contained in the dental material) contained in the test material in the test solution and the relative cell growth rate (%) of the dental material are determined by the above-mentioned first aspect of the present invention. It may be the same as in the case of the monomer composition for dental materials.

[Manufacturing method of dental materials]
It has the above-mentioned polyfunctional monomer for dental materials according to the first aspect of the present invention, a polymerizable monomer other than the polyfunctional monomer (for example, a (meth) acrylate group-containing monomer other than the polyfunctional monomer of the present invention, and an epoxy group. The method for producing the dental material according to the first aspect of the present invention by mixing a monomer), a polymerization initiator, a filler, other components and the like is not particularly limited as long as it is a known method.

[Cured product]
The dental material of the first aspect of the present invention can be cured under appropriate conditions according to the polymerization method of the above-mentioned polymerization initiator. For example, in the case of the dental material of the first aspect of the present invention containing a photopolymerization initiator by visible light irradiation, after processing the dental material into a predetermined shape, a predetermined light irradiation device is used. A desired cured product can be obtained by irradiating with visible light for a period of time. Conditions such as irradiation intensity can be appropriately changed according to the curability of the dental material. Further, the mechanical properties of the cured product can be improved by heat-treating the cured product cured by light irradiation such as visible light under more appropriate conditions. As another example, in the case of the dental material of the first aspect of the present invention containing a polymerization initiator by heating, the dental material is processed into a predetermined shape and then heated at an appropriate temperature and time. Therefore, a desired cured product can be obtained.
The cured product of the dental material of the first aspect of the present invention obtained as described above may be used for dental treatment.

[how to use]
The method of using the dental material according to the first aspect of the present invention is not particularly limited as long as it is generally known as the method of using the dental material. For example, when the dental material of the first aspect of the present invention is used as a composite resin for filling a caries cavity, the dental material is filled in the cavity in the oral cavity and then photo-cured using a known light irradiation device. , Achieve the purpose. When used as a composite resin for crown restoration, it is desired to process it into an appropriate shape, photo-cure it using a known light irradiation device, and if necessary, heat-treat it under predetermined conditions. Crown restoration material can be obtained.

[Use]
The dental material of the first aspect in the present invention can be suitably used for dental treatment applications, for example, a filling composite resin, a crown hard resin, a denture base resin, a denture base lining material, an impression material, and the like. Dental Adhesives (Orthodontic Adhesives, Bonding Materials (Is This More General), Adhesive Resin Cementes, Filling Adhesive Composite Resins, and Resin Additive Glass Ionomer Cements), Dental Primers, Tooth Fracture Grooves Examples include sealing materials, CAD / CAM resin blocks, temporary crowns, and artificial dental materials.

[kit]
The kit of the first aspect of the present invention includes the dental material of the first aspect. In the kit of the first aspect of the present invention, each component of the dental material is divided into two or more agents in consideration of a kit in which each component of the dental material is filled as one agent, a polymerization form, storage stability and the like. Examples thereof include a kit composed of a plurality of filled agents. In addition, such a kit may contain other dental materials to be used at the same time other than the dental materials of the first aspect of the present invention.

[Hydroxy group-containing monomer for dental materials]
The hydroxyl group-containing monomer for dental materials according to the second aspect of the present invention has the following general formula (8B) in which the following core portion (X) and the following terminal group (Y2B) are bonded directly or via the following linking group (Z). It is a compound indicated by.

上記一般式（８Ｂ）中、ｎ^8aBは核部（Ｘ）に対して直接結合している末端基（Ｙ２Ｂ）の数を示し、ｎ^8bBは核部（Ｘ）に対して連結基（Ｚ）を介して結合している末端基（Ｙ２Ｂ）の数を示し、ｎ^8aBおよびｎ^8bBの和は核部（Ｘ）の価数に等しい。ｎ^8aBおよびｎ^8bBは０以上の整数であり、その和が３以上であればその組み合わせには特に制限がない。組み合わせの一例としては、ｎ^8aBが０であれば、ｎ^8bBは３以上の整数となり、この場合は、全ての末端基（Ｙ２Ｂ）は核部Ｘに連結基（Ｚ）を介して結合している。また、別の組み合わせの一例としては、ｎ^8bBが０であれば、ｎ^8aBは３以上の整数となり、この場合は、全ての末端基（Ｙ２Ｂ）は核部Ｘに直接結合している。

In the above general formula (8B), n ^8aB indicates the number of terminal groups (Y2B) directly bonded to the ^{nucleus (X), and n 8bB} is the linking group (Z) to the nucleus (X). Indicates the number of terminal groups (Y2B) attached via, ^{and the sum of n 8aB} and n ^8bB is equal to the valence of the nucleus (X). n ^8aB and n ^8bB are integers of 0 or more, and the combination is not particularly limited as long as the sum is 3 or more. As an example of the combination ^{, if n 8aB} is 0, n ^8bB is an integer of 3 or more. In this case, all the terminal groups (Y2B) are bonded to the core X via the linking group (Z). There is. Further, as an example of another combination ^{, if n 8bB} is 0, n ^8aB is an integer of 3 or more, and in this case, all the end groups (Y2B) are directly bonded to the nuclear portion X.

[Nuclear part (X)]
The core portion (X) is a trivalent or higher valent organic group containing an oxygen atom or a nitrogen atom and the atom bonded to the terminal group (Y2B) or the linking group (Z) is an oxygen atom or a nitrogen atom. .. The oxygen atom or nitrogen atom bonded to the terminal group (Y2B) or the linking group (Z) is a methylene group or a divalent aromatic carbon group other than the terminal group (Y2B) or the linking group (Z). It is combined. Any hydrogen atom contained in the methylene group or the divalent aromatic carbon group may be replaced with a monovalent hydrocarbon group having 1 to 12 carbon atoms. The number of carbon atoms in the core portion (X) is usually in the range of 1 to 200, but is preferably 1 to 100, more preferably 1 to 30, and even more preferably 2 to 20.

The valence of the core portion (X) is 3 or more as described above, but is preferably 3 to 12 valences, and more preferably 3 to 8 valences. The atom bonded to the terminal group (Y2B) or the linking group (Z) is selected from an oxygen atom or a nitrogen atom as described above, but is preferably an oxygen atom. Examples of the core portion (X) include groups represented by the above general formulas (6a) to (6j) exemplified as the core portion (X) of the polyfunctional monomer for dental materials.

[Terminal group (Y2B)]
The terminal group (Y2B) is a (meth) acryloyl group-containing group (Y3) represented by the above general formula (9) described as a (meth) acryloyl group-containing group (Y3) contained in a polyfunctional monomer for dental materials. It is a (meth) acryloyl group or a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of terminal groups (Y2B) may be the same or different, except that all of the compounds represented by the general formula (8B). Of the terminal groups (Y2B), one or more are (meth) acryloyl group-containing groups (Y3) and one or more are hydrogen atoms.

The (meth) acryloyl group-containing group (Y3) represented by the general formula (9) is exemplified as a specific example of the (meth) acryloyl group-containing group (Y3) contained in the polyfunctional monomer for dental materials. , The groups represented by the above general formulas (9a) to (9f) can be mentioned.

The terminal group (Y2B) is a (meth) acryloyl group-containing group (Y3), a (meth) acryloyl group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom represented by the above general formula (9) as described above. However, it is preferably a (meth) acryloyl group-containing group (Y3) or a hydrogen atom.

[Connecting group (Z)]
The linking group (Z) is the same as the divalent group represented by the general formula (2) described as the linking group (Z) contained in the polyfunctional monomer for dental materials, and is represented by the above general formula (8B). When a plurality of linking groups (Z) are contained in the compound, the linking groups (Z) may be the same or different.

^{The definitions and preferred embodiments of n 2a} , n ^2b , n ^2c , and n ^{2d in} the general formula (2) are the same as for the polyfunctional monomer for dental materials. In the case of the hydroxyl group-containing monomer for dental materials, the left end of the group represented by the general formula (2) is bonded to the core portion (X), and the right end of the group is bonded to the terminal group (Y2B).

_{Explanation of the repeating unit represented by -C 2} H ₄ O- in the above general formula (2), description of the repeating unit represented by -C ₃ H ₆ O-, and the repeating unit represented by -C ₄ H ₈ O-. The description regarding the repeating unit indicated by −CO (CH ₂ ) ₅ O− is the same as that for the polyfunctional monomer for dental materials.

The linking group (Z) is preferably a divalent group represented by the above general formula (4) described as a preferable example of the linking group (Z) contained in the polyfunctional monomer for dental materials. When a plurality of linking groups (Z) are contained in the compound represented by the general formula (8B), the linking groups (Z) may be the same or different.

^{The definitions and preferred embodiments of n 4a} , n ^4b and n ^{4c in} the general formula (4) are the same as in the case of the polyfunctional monomer for dental materials. In the case of the hydroxyl group-containing monomer for dental materials, the left end of the group represented by the general formula (2) is bonded to the core portion (X), and the right end of the group is bonded to the terminal group (Y2B). The description of each repeating unit in the general formula (4) is the same as the description of each repeating unit in the general formula (2).

The linking group (Z) is more preferably a divalent group represented by the above general formula (5) described as a preferable example of the linking group (Z) contained in the polyfunctional monomer for dental materials. When a plurality of linking groups (Z) are contained in the compound represented by the general formula (8B), the linking groups (Z) may be the same or different.

^{The definitions and preferred embodiments of n 5a} and n ^{5b in} the general formula (5) are the same as in the case of the polyfunctional monomer for dental materials. In the case of the hydroxyl group-containing monomer for dental materials, the left end of the group represented by the general formula (2) is bonded to the core portion (X), and the right end of the group is bonded to the terminal group (Y2B). The description of each repeating unit in the general formula (5) is the same as the description of each repeating unit in the general formula (2).

A more specific example of the linking group (Z) is that the repeating unit is composed of only the oxyethylene unit (in the general formula (5), n ^5b is 0 and n ^5a is 1 to 100. , Preferably from 1 to 20), those composed only of oxypropylene units (in the general formula (5), n ^5a is 0 and n ^5b is 1 to 100, preferably 1 to 20). , Polymer block composed of oxypropylene unit-Polymer block composed of oxyethylene unit-Polymer block composed of oxypropylene unit (in the general formula (5), the structure of the following (5') Those having a structure connected by) and the like can be mentioned.

上記一般式（５'）中、ｎ^5a1、ｎ^5a2およびｎ^5bは、各繰り返し単位のユニット数を示し、それぞれ１〜１００であり、好ましくは１〜２０である。ｎ^5a1、ｎ^5a2およびｎ^5bの合計は、１〜１００であり、好ましくは１〜２０である。上記基の左端は核部（Ｘ）と結合しており、上記基の右端は末端基（Ｙ２Ｂ）と結合しており、括弧内のオキシプロピレン重合体ブロック、オキシエチレン重合体ブロックはこの順に結合している。上記一般式（５'）中の各繰り返し単位に関する説明は、上記一般式（２）中の各繰り返し単位の説明と同一である。

In the above general formula (5'), n ^5a1 , n ^5a2, and n ^5b indicate the number of units of each repeating unit, which is 1 to 100, preferably 1 to 20, respectively. The sum of n ^5a1 , n ^5a2 and n ^5b is 1 to 100, preferably 1 to 20. The left end of the group is bonded to the nucleus (X), the right end of the group is bonded to the terminal group (Y2B), and the oxypropylene polymer block and the oxyethylene polymer block in parentheses are bonded in this order. doing. The description of each repeating unit in the general formula (5') is the same as the description of each repeating unit in the general formula (2).

[Manufacturing method of hydroxyl group-containing monomer for dental materials]
The polyfunctional monomer for dental materials of the present invention has, for example, the following general formula (1B) in which the following core portion (X) and the following terminal group (Y1B) are bonded directly or via the following linking group (Z). Obtained by reacting at least one of the active protons in the compound shown with the isocyanate group in the (meth) acryloyl group-containing isocyanate compound represented by the following general formula (3) to form the corresponding carbamate group or urea group. Be done. However, among the above-mentioned active protons, at least one active proton remains unreacted. The active proton referred to here refers to a hydrogen atom that binds to alcoholic oxygen and amine nitrogen and has reactivity with isocyanate at a practical rate.

The conditions for producing the polyfunctional monomer for dental materials of the present invention are, for example, the following general formula in which the following core portion (X) and the following terminal group (Y1B) are bonded directly or via the following linking group (Z). The isocyanate group contained in the compound represented by the following general formula (3) of the raw material containing the compound represented by 1B) and the raw material containing the (meth) acryloyl group-containing isocyanate compound represented by the following general formula (3). ) / (Number of active protons bonded to oxygen and nitrogen atoms contained in the compound represented by the following general formula (1B)) (hereinafter referred to as the reaction ratio at the time of production) <1 is there. At this time, the reaction ratio at the time of the above production is (1 / (the number of active protons bonded to oxygen atoms and nitrogen atoms contained in the compound represented by the following general formula (1B) (compound'(1B) in one molecule). The average number of active protons))) or more is preferable. In this case, in terms of reaction amount theory, some of the active protons in the compound represented by the following general formula (1B) remain in the reaction product. It becomes.

The number of moles of active protons in a raw material containing a compound represented by the following general formula (1B) is determined by a known analysis method, for example, measurement of hydroxyl value, specifically JIS K 0070-1992, JIS K 1557-1-2007. , ISO 14900-2001 and methods conforming to these, etc., can be obtained by calculation. The number of moles of isocyanate groups contained in the compound represented by the following general formula (3) is determined by a known analysis method, for example, measurement of NCO value, specifically JIS K 7301-1995, JIS K 1603-2007, JIS. It can be obtained by calculation from K 1556-2006, ISO 14896-2006 and methods conforming to these.

上記一般式（１Ｂ）中、ｎ^1aBは核部（Ｘ）に直接結合している末端基（Ｙ１Ｂ）の数を示し、ｎ^1bBは核部（Ｘ）に連結基（Ｚ）を介して結合している末端基（Ｙ１Ｂ）の数を示し、ｎ^1aBおよびｎ^1bBの和は、核部（Ｘ）の価数に等しい。ｎ^1aBおよびｎ^1bBは０以上の整数であり、その和が３以上であればその組み合わせには特に制限がない。組み合わせの一例としては、ｎ^1aBが０であれば、ｎ^1bBは３以上の整数となり、この場合は、全ての末端基（Ｙ１Ｂ）は核部Ｘに連結基（Ｚ）を介して結合している。また、別の組み合わせの一例としては、ｎ^1bBが０であれば、ｎ^1aBは３以上の整数となり、この場合は、全ての末端基（Ｙ２Ｂ）は核部Ｘに直接結合している。核部（Ｘ）および連結基（Ｚ）の説明は、上述一般式（８Ｂ）に対する説明のとおりである。

In the above general formula (1B), n ^1aB indicates the number of terminal groups (Y1B) directly attached to the ^{nucleus (X), and n 1bB} is attached to the nucleus (X) via a linking group (Z). The number of terminal groups (Y1B) is shown, ^{and the sum of n 1aB} and n ^1bB is equal to the valence of the nucleus (X). n ^1aB and n ^1bB are integers of 0 or more, and the combination is not particularly limited as long as the sum is 3 or more. As an example of the combination ^{, if n 1aB} is 0, n ^1bB is an integer of 3 or more. In this case, all the terminal groups (Y1B) are bonded to the core X via the linking group (Z). There is. Further, as an example of another combination ^{, if n 1bB} is 0, n ^1aB is an integer of 3 or more, and in this case, all the end groups (Y2B) are directly bonded to the core portion X. The description of the core portion (X) and the linking group (Z) is as described with respect to the above general formula (8B).

[Terminal group (Y1B)]
The terminal group (Y1B) is a (meth) acryloyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom, and a plurality of Y1Bs may be the same or different. However, two or more of the terminal groups (Y1B) contained in the compound represented by the above general formula (1B) are hydrogen atoms. The terminal group (Y1B) is preferably a (meth) acryloyl group or a hydrogen atom, and more preferably composed of only a hydrogen atom.

[Specific example of the compound of the general formula (1B)]
Examples of the compound of the general formula (1B) include the above general formulas (6'a) to (6'a), which are exemplified as specific examples of the compound of the general formula (1A) used for producing a polyfunctional monomer for dental materials. Examples thereof include the polyhydric alcohol represented by 6'h).

^{The definition and preferred examples of n 6'g in} the general formula (6'g) are the same as in the case of the compound of the general formula (1A).

Further, as another example of the compound of the general formula (1B), for example, the above-mentioned general formula (1A) exemplified as a specific example of the compound of the general formula (1A) used for producing a polyfunctional monomer for dental materials. Examples thereof include the polyols represented by 6'i) to (6'k).

^{Definitions and preferred embodiments of n 6'ia} , n ^6'ja , and n ^{6'ka in} the general formulas (6'i), (6'j), and (6'k), the general formula (6'i). and definitions and preferred aspects of the n ^6'Ib and n ^6'Jb in (6'j), defined and preferred aspects of the n ^6'Kb and n ^6'Kc in the general formula (6'k), the general formula The definitions and specific examples of X in (6'i), (6'j), and (6'k) are the same as for the compound of general formula (1A) used in the production of polyfunctional monomers for dental materials. is there.

Some polyols having repeating units such as oxyethylene units and oxypropylene units in the molecule have already been widely used in the industrial world as materials for polyurethane and the like. The production method is not particularly limited, but it can be obtained by adding ethylene oxide, propylene oxide or the like to the polyols represented by the general formulas (6'a) to (6'h) by a known method.

[(Meta) acryloyl group-containing isocyanate compound]

上記一般式（３）中、Ｒ^3aは水素原子またはメチル基を示し、Ｒ^3bは、炭素数２〜６の直鎖アルキレン基、または炭素数２〜６の直鎖オキシアルキレン基を示し、該直鎖アルキレン基または該直鎖オキシアルキレン基に含まれる水素原子は炭素数１〜６のアルキル基または（メタ）アクリロイルオキシメチレン基で置換されていてもよい。

In the above general formula (3), R ^3a represents a hydrogen atom or a methyl group, and R ^3b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.

As a specific example of the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3), as a preferable example of the compound represented by the general formula (3) used for producing a polyfunctional monomer for dental materials. At least one selected from the group consisting of the compounds represented by the above general formulas (3a) to (3f) described can be mentioned.

These (meth) acryloyl group-containing isocyanate compounds may be used alone or in admixture of two or more.

[Reaction conditions]
The hydroxyl group-containing monomer for dental materials of the present invention can be obtained by reacting the compound represented by the general formula (1B) as described above with the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). However, the reaction can be carried out by a known or known method.

For example, the hydroxyl group-containing monomer for dental materials of the present invention can be obtained by mixing the compound represented by the general formula (1B) with the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). it can. At this time, the hydroxyl group or amino group in the compound represented by the general formula (1B) reacts with the isocyanate group in the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) to form a carbamoyl group. Alternatively, a urea group is generated. Such a reaction is sometimes called a urethanization reaction.

At the time of the reaction, a catalyst may or may not be added, but it is preferable to add a catalyst in order to improve the reaction rate. As the catalyst, a known catalyst that accelerates the urethanization reaction can be used.

Specific examples of the urethanization catalyst are the same as in the case of producing a polyfunctional monomer for dental materials. Among these, dibutyltin dilaurate and tin octanate, which proceed with the reaction in a small amount and have high selectivity for the diisocyanate compound, are preferable.

When a urethanization catalyst is used, the total weight of the compound represented by the general formula (1B) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is 100 parts by weight. It is preferable to add 001 to 0.5 parts by weight, more preferably 0.002 to 0.3 parts by weight, further preferably 0.01 to 0.3 parts by weight, and 0. It is more preferable to add 01 to 0.2 parts by weight, and even more preferably 0.05 to 0.2 parts by weight. If the addition amount is less than the above lower limit value, the effect of the catalyst may be small and the reaction time may be significantly lengthened. If the addition amount exceeds the above upper limit value, the catalyst effect becomes excessive and a large amount of reaction heat is generated and the temperature. It can be difficult to control. The entire amount of the catalyst may be added at the start of the reaction, or may be added to the reaction system sequentially or divided as needed. Such sequential or divided catalyst injection suppresses the generation of a large amount of heat of reaction at the initial stage of the reaction, which makes it easier to control the reaction temperature.

The reaction temperature is not particularly limited, but is preferably 0 to 120 ° C, more preferably 20 to 100 ° C, and even more preferably 40 to 80 ° C. If the reaction is carried out at a temperature lower than the above lower limit, the reaction rate is extremely lowered, so that it takes a very long time to complete the reaction, and in some cases, the reaction may not be completed. On the other hand, if the reaction is carried out at a temperature exceeding the above upper limit value, impurities may be generated by a side reaction. Such impurities may cause coloring of the produced hydroxyl group-containing monomer for dental materials.

The reaction temperature is preferably controlled from the viewpoint of stable production in the above-mentioned preferable temperature range. Since the urethanization reaction is usually an exothermic reaction, cooling may be performed when the calorific value is large and the temperature of the reactant may rise beyond a preferable reaction temperature range. Further, when the reaction is almost completed and the temperature of the reaction product may drop beyond the preferable reaction temperature range, heating may be performed.

The hydroxyl group-containing monomer for dental materials of the present invention has polymerization activity. Therefore, during its production, an unintended polymerization reaction may proceed when exposed to high temperatures. In order to prevent such an unintended polymerization reaction, a known polymerization inhibitor can be added before or during the reaction. The polymerization inhibitor is not particularly limited as long as it can suppress unintended polymerization of the (meth) acryloyl group in the production of the hydroxyl group-containing monomer for dental materials of the present invention, and specific examples and suitable examples thereof are polyfunctional monomers for dental materials. It is the same as the case of manufacturing. The amount of the polymerization inhibitor to be added is not particularly limited, but is based on 100 parts by weight of the total weight of the compound represented by the general formula (1B) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). , 0.001 to 0.5 parts by weight, more preferably 0.002 to 0.3 parts by weight, and even more preferably 0.005 to 0.3 parts by weight. , 0.005 to 0.1 parts by weight is more preferable, and 0.01 to 0.1 parts by weight is further preferable. If the addition amount is less than the above lower limit value, the ability as a polymerization inhibitor may not be exhibited, and if the addition amount exceeds the above upper limit value, it is cured when used as a dental material which is an application of a hydroxyl group-containing monomer for dental materials. The speed may be extremely slow, limiting its practicality.

A solvent may be used during the urethanization reaction. The solvent has no practical reactivity with the compound represented by the general formula (1B) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3), does not inhibit the reaction, and is a raw material and a product. It is not particularly limited as long as it dissolves a substance. Further, the reaction may be carried out without using a solvent. Since the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is usually a low-viscosity liquid, it can be miscible with the compound represented by the general formula (1B) without using a solvent. Can react to.

The method for mixing the compound represented by the general formula (1B) with the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is not particularly limited. For example, a method of adding and mixing the compound represented by the general formula (1B) in the reaction vessel while controlling the input amount of the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3). A method of adding and mixing the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) in the reaction vessel while controlling the input amount of the compound represented by the general formula (1B). A method of simultaneously adding and mixing the compound represented by the general formula (1B) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) to the reaction vessel while controlling the input amount. There is. According to such a mixing method, the amount of heat generated by the urethanization reaction can be controlled within an appropriate range, so that the temperature control during the reaction becomes easy. Further, the urethanization reaction is carried out by putting the compound represented by the general formula (1B) and the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) in a total amount in a reaction vessel and then raising the temperature. The method can also be adopted. During the reaction, the reaction temperature may rise sharply due to the heat of reaction, so it may be necessary to control the temperature by cooling as appropriate.

Oxygen is effective as a polymerization inhibitor for compounds containing (meth) acryloyl groups. Therefore, during the reaction, oxygen may be introduced into the reactor to prevent unintended (meth) acryloyl group polymerization. The specific mode and preferred mode of oxygen introduction are the same as in the case of producing a polyfunctional monomer for dental materials.

If water is present as an impurity in the system during the urethanization reaction, the (meth) acryloyl group-containing isocyanate compound represented by the above general formula (3) may react with water to generate an unintended impurity. Therefore, it is preferable that water does not exist in the reaction system as much as possible during the urethanization reaction.

Therefore, the water content of the compound represented by the general formula (1B) is preferably as small as possible, and specifically, the water content is 0.5 with respect to the compound represented by the general formula (1B). It is preferably 0% by weight or less, more preferably 0.3% by weight or less, and further preferably 0.1% by weight or less. When the amount of water contained in the compound represented by the general formula (1B) exceeds the above value, it is preferable to remove the water by a known method and then use it as a raw material for the hydroxyl group-containing monomer for dental materials of the present invention. .. Further, it is preferable that the inside of the reaction vessel where the urethanization reaction is carried out is dried by a known method to remove water.

[Monomer composition for dental materials containing a hydroxyl group-containing monomer for dental materials]
The hydroxyl group-containing monomer for dental materials according to the second aspect of the present invention can be used as a monomer composition for dental materials by blending other components, for example, components other than polyfunctional monomers suitable for dental materials. .. This monomer composition for dental materials can be blended with a dental material described later, and is a polymerizable monomer other than the hydroxyl group-containing monomer for dental materials of the second aspect of the present invention (for example, (meth) other than the hydroxyl group-containing monomer of the present invention). An acrylate group-containing monomer) may be contained.

In the dental material monomer composition according to the second aspect of the present invention, for example, the content of the dental material hydroxyl group-containing monomer according to the second aspect of the present invention is 1.0 mass by mass with respect to the entire dental material monomer composition. % Or more (10% by mass or more, 50% by mass or more, 80% by mass or more, 90% by mass or more, etc.), 100% by mass or less (99% by mass or less, 90% by mass or less, 80% by mass or less, 50% mass or more) Hereinafter, it may be 10% by mass or less).

It is desirable that the monomer composition for dental materials according to the second aspect of the present invention shows a negative result in the reversion mutation test. The test method of the reversion mutation test (Ames test) is the method of the reversion mutation test of the monomer composition for dental material of the first aspect of the present invention described above, wherein the monomer composition for dental material of the first aspect of the present invention. Is replaced with the monomer composition for dental materials according to the second aspect of the present invention, and the procedure is the same.

(Cell test by NRU method)
The monomer composition for dental materials according to the second aspect of the present invention may have a relative cell viability within a certain range in a cell test by the NRU method using Balb / 3T3 cells. The cell test is carried out in the same procedure as the above-mentioned cell test by the NRU method, in which the monomer composition for dental materials according to the first aspect of the present invention is replaced with the monomer composition for dental materials according to the second aspect of the present invention. .. Further, the concentration of the test substance (monomer containing hydroxyl group for dental material contained in the monomer composition for dental material) contained in the test composition in the test solution and the relative cell growth rate (%) of the monomer composition for dental material are determined. It may be the same as that in the case of the above-mentioned monomer composition for dental materials according to the first aspect of the present invention.

(Cell test by WST method)
The monomer composition for dental materials according to the second aspect of the present invention may have a relative cell growth rate within a certain range in a cell test by the WST method using Balb / 3T3 cells. The cell test is carried out in the same procedure as in the cell test by the WST method described above, replacing the monomer composition for dental materials of the first aspect of the present invention with the monomer composition for dental materials of the second aspect of the present invention. .. Further, the concentration of the test substance (monomer containing hydroxyl group for dental material contained in the monomer composition for dental material) contained in the test composition in the test solution and the relative cell growth rate (%) of the monomer composition for dental material are determined. It may be the same as that in the case of the above-mentioned monomer composition for dental materials according to the first aspect of the present invention.

[Dental materials containing hydroxyl group-containing monomers for dental materials]
The hydroxyl group-containing monomer for dental materials, which is the second aspect of the present invention, is suitable as a raw material for dental materials. In contrast to the hydroxyl group-containing monomer for dental materials of the present invention, a component other than the hydroxyl group-containing monomer for dental materials of the present invention (for example, a polymerizable monomer other than the hydroxyl group-containing monomer for dental materials of the present invention (hydroxyl-containing monomer of the present invention) By blending other (meth) acrylate group-containing monomer, epoxy group-containing monomer, etc.), a dental material containing the hydroxyl group-containing monomer for dental material of the present invention can be produced.

[(Meta) acrylate group-containing monomer other than the hydroxyl group-containing monomer for dental materials of the present invention]
As an example of the component other than the hydroxyl group-containing monomer for dental materials of the present invention, a (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention can be mentioned.

The (meth) acrylate group-containing monomer other than the above-mentioned hydroxyl group-containing monomer of the present invention contains one or more (meth) acrylate groups in the molecule. The number of polymerizable groups contained may be one or two or more.

The (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention may be composed of one kind of compound or a mixture of two or more kinds of compounds.
Examples of the (meth) acrylate group-containing monomer other than the above-mentioned hydroxyl group-containing monomer having only one polymerizable group are represented by the above general formula (21) exemplified as a monomer that can be used together with a polyfunctional monomer for dental materials. Examples include monomers. (However, among the monomers represented by the general formula (21), the monomers corresponding to the hydroxyl group-containing monomers for dental materials of the present invention are excluded.).

Specific examples of the monovalent organic group that can be R ^{21b of the} general formula (21) are the same as those of the monomer represented by the general formula (21) that can be used together with the polyfunctional monomer for dental materials.

Specific examples of the compound having a methacryloyl group represented by the general formula (21) are the same as those of the monomer represented by the general formula (21) that can be used together with the polyfunctional monomer for dental materials.

Specific examples of the compound having an acryloyl group represented by the general formula (21) are the same as those of the monomer represented by the general formula (21) that can be used together with the polyfunctional monomer for dental materials.

Examples of the (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention having two or more polymerizable groups include (meth) other than the polyfunctional monomer for dental materials that can be used together with the polyfunctional monomer for dental materials. ) Examples of the acrylate group-containing monomer include the monomers represented by the above general formula (22) (however, among the monomers represented by the general formula (22), the monomers corresponding to the hydroxyl group-containing monomers for dental materials of the present invention. Excludes.)

Specific examples of the divalent organic group that can be R ^{22c of the} general formula (22) are the same as those of the monomer represented by the general formula (22) used together with the polyfunctional monomer for dental materials.

Among the monomers represented by the general formula (22), an example of a suitable monomer is a monomer in which R ^22c is a linear alkylene group having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms.

Specific examples of the above-mentioned suitable monomer and the compound having a methacryloyl group are the same as in the case of the monomer represented by the general formula (22) which can be used together with the polyfunctional monomer for dental materials.

Specific examples of the above-mentioned suitable monomer and the compound having an acryloyl group are the same as those of the monomer represented by the general formula (22) which can be used together with the polyfunctional monomer for dental materials.

Further, among the monomers represented by the general formula (22), as another example of a suitable monomer, R ^22C is a linear oxyalkylene group having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms. Monomers can be mentioned.

Specific examples of the above-mentioned suitable monomer and the compound having a methacryloyl group are the same as in the case of the monomer represented by the general formula (22) which can be used together with the polyfunctional monomer for dental materials.

Specific examples of the above-mentioned suitable monomer and the compound having an acryloyl group are the same as those of the monomer represented by the general formula (22) which can be used together with the polyfunctional monomer for dental materials.

Further, among the monomers represented by the general formula (22), as a suitable monomer and other examples, the carbamoyl group represented by the general formula (23) exemplified as a monomer that can be used together with a polyfunctional monomer for dental materials is used. Examples include the monomers having.

Specific examples of the divalent organic group which can be R ^23c and R ^{23d of the} general formula (23) are the same as those of the monomer represented by the general formula (23) which can be used together with the polyfunctional monomer for dental materials.

Specific examples of the divalent organic group having 1 to 20 carbon atoms which may contain oxygen which can be R ^{23e of the} general formula (23) are shown by the general formula (23) which can be used together with the polyfunctional monomer for dental materials. This is the same as in the case of the monomer.

Specific examples of the compound having an acryloyl group represented by the general formula (23) are the same as those of the monomer represented by the general formula (23) that can be used together with the polyfunctional monomer for dental materials.

The compounds exemplified as a suitable alternative example of the compound having a (meth) acryloyl group represented by the above general formula (23) can be used together with the polyfunctional monomer for dental materials, the above general formulas (24a) to (24e). At least one selected from the group consisting of the compounds represented by.

Further, as another example of the preferable compound represented by the general formula (22), the compound of the above general formula (25), which can be used together with the polyfunctional monomer for dental materials, can be mentioned.

Specific examples of the divalent organic group having 1 to 20 carbon atoms which may contain oxygen which can be R ^{25e of the} general formula (25) are the general formula (25) which can be used together with the polyfunctional monomer for dental materials. The same is true for the indicated monomers.

Specific examples of the compound having a methacryloyl group represented by the general formula (25) are the same as those of the monomer represented by the general formula (25) that can be used together with the polyfunctional monomer for dental materials.

Specific examples of the compound having an acryloyl group represented by the general formula (25) are the same as those of the monomer represented by the general formula (25) that can be used together with the polyfunctional monomer for dental materials.

Further, when the dental material containing the hydroxyl group-containing monomer for dental materials of the present invention is used for the use of a dental adhesive, it can be adhered as a (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention. It is preferable that a monomer that exerts a function is contained. Examples of the (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention exhibiting such an adhesive function include a monomer having at least one polymerizable group selected from a methacryloyl group and an acryloyl group and an acidic group. Be done. Examples of the acidic group include a phosphoric acid residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, a sulfonic acid residue and the like.

Specific examples of the monomer having a methacryloyl group and a phosphoric acid residue are the same as those of a specific example of a monomer having a methacryloyl group and a phosphoric acid residue that can be used together with a polyfunctional monomer for dental materials.

Specific examples of the monomer having an acryloyl group and a phosphoric acid residue are the same as those of a monomer having an acryloyl group and a phosphoric acid residue that can be used together with a polyfunctional monomer for dental materials.

Examples of the monomer having a methacryloyl group and a pyrophosphate residue include di (2-methacryloyloxyethyl) pyrophosphate and acid chlorides thereof.
Examples of the monomer having an acryloyl group and a pyrophosphate residue include di (2-acryloyloxyethyl) pyrophosphate and acid chlorides thereof.

Examples of the monomer having a methacryloyl group and a thiophosphate residue include 2-methacryloyloxyethyl dihydrogendithiophosphate, 10-methacryloyloxydecyldihydrogenthiophosphate, and acid chlorides thereof.

Examples of the monomer having an acryloyl group and a thiophosphate residue include 2-acryloyloxyethyl dihydrogendithiophosphate, 10-acryloyloxydecyldihydrogenthiophosphate, and acid chlorides thereof.

Examples of the monomer having a methacryloyl group and a carboxylic acid residue include 4-methacryloyloxyethoxycarbonylphthalic acid, 5-methacryloylaminopentylcarboxylic acid, 11-methacryloyloxy-1,1-undecandicarboxylic acid, and these acids. Examples include chlorides and acid anhydrides.

Examples of the monomer having an acryloyl group and a carboxylic acid residue include 4-acryloyloxyethoxycarbonylphthalic acid, 5-acryloylaminopentylcarboxylic acid, 11-acryloyloxy-1,1-undecandicarboxylic acid, and these acids. Examples thereof include chlorides and acid anhydrides.

Examples of the monomer having a methacryloyl group and a sulfonic acid residue include 2-sulfoethyl methacrylate and 2-methacrylamide-2-methylpropanesulfonic acid.

Examples of the monomer having an acryloyl group and a sulfonic acid residue include 2-sulfoethyl acrylate and 2-acrylamide-2-methylpropane sulfonic acid.

[Polymerization initiator]
As another example of the components other than the hydroxyl group-containing monomer for dental materials of the present invention contained in the dental material of the second aspect of the present invention, a polymerization initiator can be mentioned. Specific examples, preferred examples, etc. of the polymerization initiator are the same as those of the polymerization initiator that can be contained in the dental material of the first aspect of the present invention.

The polymerization initiator or photopolymerization initiator can be used alone or in combination of two or more as appropriate, and the blending amount is usually 0.01 to 20 parts by weight, preferably 0. It is used in the range of 1 to 5 parts by weight.

[Filler]
As another example of the components other than the hydroxyl group-containing monomer for dental materials of the present invention contained in the dental material of the second aspect of the present invention, a filler can be mentioned. Specific examples, preferred examples, and the like of the filler are the same as those of the filler that can be contained in the dental material of the first aspect of the present invention.

These fillers can be added as appropriate depending on the use of the dental material. When these fillers are used, these fillers are appropriately used alone or in combination of two or more. The preferred range of the filler content varies depending on the application. For example, in the case of a dental bonding material application which is one of the dental adhesives, about 0.1 to 5 parts by weight may be contained in 100 parts by weight of the dental material in order to adjust the consistency. .. As another example, in the case of dental adhesive cement, which is one of the dental adhesives, 30 to 70 parts by weight in 100 parts by weight of the dental material is used to improve the mechanical strength and adjust the consistency. May be contained to some extent. As another example, in the case of a dental adhesive composite resin, which is one of the dental adhesives, 50 to 90 parts in 100 parts by weight of the dental material are used to improve the mechanical strength and adjust the consistency. It may be contained in an amount of about a part by weight.

[Other ingredients]
The dental material of the second aspect of the present invention is a polymerizable monomer other than the above-mentioned hydroxyl group-containing monomer for dental materials of the present invention and the hydroxyl group-containing monomer of the present invention (for example, a (meth) acrylate other than the hydroxyl group-containing monomer of the present invention. Ingredients other than the group-containing monomer (monomer having an epoxy group), the polymerization initiator, and the filler may be appropriately contained depending on the intended purpose. For example, the above-mentioned polymerization inhibitor may be contained in order to improve storage stability. In addition, pigments such as known pigments and dyes may be included in order to adjust the color tone. Further, in order to improve the strength of the cured product, a known reinforcing material such as fiber may be included. In addition, if necessary, a solvent such as acetone, ethanol, or water may be contained.

[Ratio of each component]
The amount of the hydroxyl group-containing monomer for dental materials, which is the second aspect of the present invention, to be blended in the dental material is not particularly limited, but is, for example, in the range of 0.1 to 99%. The preferred blending amount may vary depending on the application for the dental material, but for example, a polymerizable monomer component (for example, a polymerizable monomer other than the above-mentioned hydroxyl group-containing monomer for dental material and the above-mentioned hydroxyl group-containing monomer for dental material (for example). 1 to 50% by weight, more preferably 1 to 40% by weight, still more preferably 3 to 30% by weight is blended in the (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention, the monomer having an epoxy group). In particular, when the use of the dental material is a dental adhesive (bonding material) or a dental primer, the blending amount of the hydroxyl group-containing monomer is preferably 1 to 50% by weight in the polymerizable monomer component. It is more preferably about 40% by weight. When the use of the dental material is a dental adhesive material (adhesive resin cement, adhesive composite resin for filling), a tooth fissure groove sealing material, the blending amount of the hydroxyl group-containing monomer is It is preferably 1 to 50% by weight, more preferably 1 to 20% by weight in the polymerizable monomer component.

(Return mutation test)
It is desirable that the dental material of the hydroxyl group-containing monomer for dental material of the second aspect of the present invention shows a negative result in the reversion mutation test. The test method of the reversion mutation test (Ames test) is the above-mentioned method of the reversion mutation test, in which the monomer composition for dental material according to the first aspect of the present invention is used as the hydroxyl group-containing monomer for dental material according to the second aspect of the present invention. Replace with the dental material of, and follow the same procedure.

(Cell test by NRU method)
The dental material of the hydroxyl group-containing monomer for dental material of the second aspect of the present invention may have a relative cell viability within a certain range in a cell test by the NRU method using Balb / 3T3 cells. In the cell test described above, in the cell test by the NRU method described above, the monomer composition for dental material according to the first aspect of the present invention is replaced with the dental material of the hydroxyl group-containing monomer for dental material according to the second aspect of the present invention. Follow the procedure. Further, the concentration of the test substance (hydroxyl-containing monomer for dental material contained in the dental material) contained in the test material in the test solution and the relative cell growth rate (%) of the dental material are determined by the above-mentioned first aspect of the present invention. It may be the same as in the case of the monomer composition for dental materials.

(Cell test by WST method)
The dental material of the hydroxyl group-containing monomer for dental material of the second aspect of the present invention may have a relative cell growth rate within a certain range in a cell test by the WST method using Balb / 3T3 cells. In the cell test described above, in the cell test by the WST method, the monomer composition for dental material according to the first aspect of the present invention is replaced with the dental material of the hydroxyl group-containing monomer for dental material according to the second aspect of the present invention. Follow the procedure. Further, the concentration of the test substance (hydroxyl-containing monomer for dental material contained in the dental material) contained in the test material in the test solution and the relative cell growth rate (%) of the dental material are determined by the above-mentioned first aspect of the present invention. It may be the same as in the case of the monomer composition for dental materials.

[Manufacturing method of dental materials]
It has the above-mentioned hydroxyl group-containing monomer for dental materials according to the second aspect of the present invention, a polymerizable monomer other than the hydroxyl group-containing monomer (for example, a (meth) acrylate group-containing monomer other than the hydroxyl group-containing monomer of the present invention, and an epoxy group. The method for producing the dental material according to the second aspect of the present invention by mixing a monomer), a polymerization initiator, a filler, other components and the like is not particularly limited as long as it is a known method.

[Cured product]
The dental material of the second aspect of the present invention can be cured under appropriate conditions according to the polymerization method of the above-mentioned polymerization initiator. For example, in the case of the dental material of the second aspect of the present invention containing a photopolymerization initiator by visible light irradiation, after processing the dental material into a predetermined shape, a predetermined light irradiation device is used. A desired cured product can be obtained by irradiating with visible light for a period of time. Conditions such as irradiation intensity can be appropriately changed according to the curability of the dental material. Further, the mechanical properties of the cured product can be improved by heat-treating the cured product cured by light irradiation such as visible light under more appropriate conditions. As another example, in the case of the dental material of the second aspect of the present invention containing a polymerization initiator by heating, the dental material is processed into a predetermined shape and then heated at an appropriate temperature and time. Therefore, a desired cured product can be obtained.
The cured product of the dental material of the second aspect of the present invention obtained as described above may be used for dental treatment.

[Use]
The dental material of the second aspect in the present invention can be suitably used for dental treatment applications, for example, a filling composite resin, a hard crown resin, a denture base resin, a denture base lining material, an impression material, and the like. Dental Adhesives (Orthodontic Adhesives, Bonding Materials, Adhesive Resin Cementes, Filling Adhesive Composite Resins, and Resin Addition Glass Ionomer Cements), Dental Primers, Tooth Fissure Closures, CAD / CAM Resin Blocks , Temporary crown, artificial tooth material and the like. The hydroxyl group-containing monomer for dental materials in the present invention has a function of improving the adhesive strength with the dentin during dental treatment, and is therefore particularly suitable for dental adhesives and dental primer applications.

Although the detailed reason why the dental material of the second aspect in the present invention is particularly suitable for dental adhesives and dental primer applications is unknown, the hydroxyl group-containing monomer for dental materials of the second aspect in the present invention is. As described above, the molecule contains both hydroxyl and (meth) acryloyl groups, and the interaction with the dentin surface via the hydroxyl group and the binding to the resin matrix via the (meth) acryloyl group. It is presumed that it has both functions. In addition, the hydroxyl group-containing monomer for dental materials according to the second aspect of the present invention has a carbamate structure in the molecule. The carbamate structure is known to exhibit an effect of imparting high mechanical properties to the urethane polymer by its aggregating action in a so-called urethane polymer, but in the molecule of the hydroxyl group-containing monomer for dental materials of the second aspect of the present invention. The carbamate structure contained may also have a favorable effect on the strength of the dental material of the second aspect in the present invention after curing. In general, improving the strength of the adhesive layer has a favorable effect on its adhesive properties.

[how to use]
The method of using the dental material according to the second aspect of the present invention is not particularly limited as long as it is generally known as the method of using the dental material. For example, when the dental material of the second aspect of the present invention is used as a bonding material, the dental material is applied to the tooth cavity in the oral cavity, dried if necessary, and irradiated with known light if necessary. After photocuring using an apparatus, the filling composite resin is filled.

Further, for example, when the dental material of the second aspect of the present invention is used as an adhesive resin cement, the tooth surface and the surface to be adhered to the prosthesis are primed with the prosthesis as necessary, and then the prosthesis is subjected to the primer treatment. The dental material of the second aspect is applied and the prosthesis is crimped to a predetermined place in the oral cavity.

Further, for example, when the dental material of the second aspect of the present invention is used as a primer for dentin, the dental material is applied to the tooth cavity in the oral cavity, dried if necessary, and if necessary. After photo-curing using a known light irradiation device, the prosthesis coated with adhesive cement is pressure-bonded to the tooth cavity.

Further, for example, when the dental material of the second aspect of the present invention is used as an adhesive composite resin for filling, the dental material is directly filled in the tooth cavity in the oral cavity and then photocured using a known light irradiation device. By doing so, the purpose can be achieved.

[kit]
The kit of the second aspect of the present invention includes the above dental materials. In the kit of the second aspect of the present invention, each component of the dental material is divided into two or more agents in consideration of a kit in which each component of the dental material is filled as one agent, a polymerization form, storage stability and the like. Examples thereof include a kit composed of a plurality of filled agents. In addition, the kit of the present invention may contain other dental materials to be used at the same time other than the dental materials of the second aspect of the present invention. Such kits are used in applications such as bonding materials, adhesive cements, primers, and adhesive composite resins.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Hereinafter, examples and comparative examples relating to the first aspect of the present invention will be given.

[Manufacturing Example 1A]
A polyol having the structural formula shown in Table 1A below (Actcol (registered trademark) manufactured by Mitsui Chemical Industries, Ltd., average molecular weight 1000, hydroxyl value) in a 100 ml four-necked flask equipped with a stirring blade, a thermometer and a reflux tube. 168 mgKOH / g) 50.0 g (OH group; 0.150 mol) and dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.073 g (1000 ppm with respect to the total reaction substrate weight) and 2,6-t-butyl- 0.073 g (1000 ppm based on the total reaction substrate weight) of 4-methylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised to 60 ° C. Subsequently, 23.3 g (0.150 mol) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Calends MOI (registered trademark)) was added dropwise over 10 minutes. The reaction temperature was maintained so as to be 75-85 ° C., and the reaction was carried out for 5 hours. When the infrared absorption spectrum IR (Spectrum Two, manufactured by PerkinElmer) of the reaction product was measured, it was confirmed that the vibration derived from the isocyanate of ^{2267 cm -1 had disappeared.} By discharging from the reactor, 71.2 g of a product containing a urethane methacrylic polyfunctional monomer 1A having the structural formula shown in Table 1A below was obtained. A part of the product was collected and the hydroxyl value was measured according to JIS K 0070-1992, and it was confirmed that it was 1 mgKOH / g or less.

[Manufacturing Examples 2A to 5A]
By performing the same synthesis operation as in Production Example 1A using the polyols shown in Table 1A instead of the polyols described in Production Example 1A, products containing polyfunctional monomers 2A to 5A having the structural formulas shown in Table 1A below are obtained. It was.

[Manufacturing Example 6A]
By performing the same synthesis operation as in Production Example 1A using 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karens AOI (registered trademark)) instead of 2-methacryloyloxyethyl isocyanate described in Production Example 1A. , A product containing the polyfunctional monomer 6 having the structural formula of Table 1A below was obtained.

[Example 1A-1]
0.37 g of the polyfunctional monomer 1A obtained in Production Example 1A, 1.94 g of the urethane acrylate compound having the following structural formula, triethylene glycol dimethacrylate (NK ester 3G manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hereinafter abbreviated as TEGDMA) 0. 12 g (0.42 mmol) was placed in a container and stirred at 50 ° C. until uniform to obtain a polymerizable monomer composition. Next, with respect to 40 parts by weight of this polymerizable monomer composition, 60 parts by weight of barium aluminum borosilicate glass filler (GM27884, particle size 1.5 μm, 1.6% silane treated product, manufactured by NEC SCHOTT Components Co., Ltd.), 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by IRGACURE TPO BASF, hereinafter abbreviated as TPO) was added and mixed by 0.2 parts to obtain a composition to be used as a dental material for a uniform paste.

[Bending strength test method]
The composition prepared above is filled in a 2 x 2 x 25 mm SUS mold, sandwiched from above with a cover film, and then used on one side with a dental visible light irradiator (α-light V, manufactured by Morita Tokyo Seisakusho Co., Ltd.). The composition was cured by irradiating with each other for 3 minutes from both sides for a total of 6 minutes. After storing the cured product in deionized water at 37 ° C for 24 hours, use a general-purpose testing machine (precision universal material testing machine 210X, manufactured by INTESCO Co., Ltd.) to bend 3 points at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min. The test was carried out. The results of the bending test of the cured product of the composition used as the dental material are shown in Table 2A.

［化合物７Ａ］

[Compound 7A]

[Example 1A-2]
A composition to be used as a dental material was obtained according to the operation of Example 1A-1 except that the polyfunctional monomer 1A was changed to the polyfunctional monomer 5A obtained in Production Example 5A. Further, the same operation as in Example 1A-1 was performed, and the result of the bending test was obtained. The results are shown in Table 2A.

[Comparative Example 1A-1]
The composition used as a dental material according to the operation of Example 1A-1 except that the polyfunctional monomer 1A obtained in Production Example 1A was not used, the amount used was replaced with TEGDMA, and the amount of TEGDMA was increased. I got something. Further, the same operation as in Example 1A-1 was performed, and the result of the bending test was obtained. The results are shown in Table 2A.

[Example 2A-1]
A composition to be used as a dental material was obtained according to the operation of Example 1A-1 except that the urethane acrylate compound 8A was used instead of the urethane acrylate compound 7A. Further, the same operation as in Example 1A-1 was performed, and the result of the bending test was obtained. The results are shown in Table 2A.

［化合物８Ａ］

[Compound 8A]

[Comparative Example 2A-1]
The composition used as a dental material according to the operation of Example 1A-3, except that the polyfunctional monomer 1A obtained in Production Example 1A was not used, the amount used was replaced with TEGDMA, and the amount of TEGDMA was increased. I got something. Further, the same operation as in Example 1A-3 was performed, and the result of the bending test was obtained. The results are shown in Table 2A.

From the results in Table 2A, the cured product of the composition used as the dental material containing the polyfunctional monomer for dental material of the first aspect of the present invention has a breaking strength and a breaking strength as compared with the cured product of the conventional composition. It can be seen that the energy is greatly improved. That is, it was suggested that the strength and toughness of the cured product of the dental material are improved by using the polyfunctional monomer for dental material of the present invention having both toughness and rigidity.

[Example 3A-1]
0.5 part by weight of TPO was added to 100 parts by weight of the polyfunctional monomer 1A obtained in Production Example 1A, and the mixture was stirred at room temperature until uniform to obtain a monomer solution. After that, light irradiation was performed for 20 seconds using a dental light irradiator (Translux 2Wave, manufactured by Heraeus Kurzer), and the polymerization rate was measured using infrared spectroscopy (IR) (Spectrum Two, manufactured by PerkinElmer). Was done. The results are shown in Table 3.
The polymerization rate (%) was calculated using the following formula.
Polymerization rate (%) = {1- (I _{X, CH} / I _{X, C = O} ) / (I _{0, CH} / I _{0, C = O} )} × 100
I _{X, CH} : Absorbance at 810 cm ^-1 (derived from acryloyl group) or 815 cm ^-1 (derived from methacryloyl group _{) after light irradiation I 0, CH} : The above values before light irradiation I _{X, C = O} : After light irradiation Absorbance at 1637 cm ^-1 (derived from carbonyl group) I _{0, C = O} : The above values before light irradiation

[Examples 3A-2 to 3A-5]
The polymerization rates of the polyfunctional monomers 2A, 3A, 4A and 6A obtained in the production example were measured by the same method as in Example 3A-1. The results are shown in Table 3A.

[Comparative Example 3A-1]
The polymerization rate of the general-purpose dental material methacrylic compound TEGDMA was measured by the same method as in Example 3A-1. The results are shown in Table 3A.

Hereinafter, examples and comparative examples relating to the second aspect of the present invention will be given.

[Manufacturing Example 1B]
Polyphenol 1B having the following structural formula in a 300 ml four-necked flask equipped with a stirring blade, a thermometer and a reflux tube (Actcol (registered trademark) manufactured by Mitsui Chemical Industry Co., Ltd., average molecular weight 182, hydroxyl value 926 mgKOH / g) 99.0 g (OH group: 1.63 mol), dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.27 g (1000 ppm based on the total reaction substrate weight) and 2,6-t-butyl-4-methylphenol (Tokyo) 0.14 g (manufactured by Kasei Kogyo Co., Ltd.) (500 ppm with respect to the total reaction substrate weight) was added, and the temperature was raised to 55 ° C. Subsequently, 171 g (1.10 mol, 2/3 equivalent to the number of OH moles of the polyol 1 used) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Calends MOI (registered trademark)) was applied over 20 minutes. Dropped. The reaction temperature was maintained so as to be 80-85 ° C., and the reaction was carried out for 8 hours. When the infrared absorption spectrum IR (Spectrum Two manufactured by PerkinElmer Co., Ltd.) was measured, it was confirmed that the vibration derived from the isocyanate of ^{2267 cm -1 had disappeared.} A part of the product was collected and the hydroxyl value was measured according to JIS K 0070. As a result, it was 119 mgKOH / g. Liquid chromatography-mass spectrometry (LC-MS analysis) of the reaction product (ACQUITY UPLC BEH C181.7 μm (2.1 mm x 10 mm) / ACQUITY UPLC H-Class-SQ Detector 2) manufactured by Japan Waters Corp. ^{Masses [MH] +} : 489 and [M-Na] ⁺ : 511 consistent with the molecular weight of compound 1B of a + b + c = 1 into which one oxyethylene unit was introduced as a product were detected. By discharging from the reactor, 260 g of a product containing a hydroxyl group-containing monomer having the structural formula of the following compound 1B was obtained.

[Manufacturing Examples 2B to 5B]
By performing the same synthesis operation as in Production Example 1B using the polyols shown in Table 1B instead of the polyols described in Production Example 1B, products containing hydroxyl group-containing monomers 2B to 5B were obtained.

[Manufacturing Example 6B]
With the exception of Production Example 1B, the polyol 6B shown in Table 1B was used instead of the polyol described in Production Example 1B, and 3/4 equivalent of Calends MOI® was reacted with the number of moles of OH of the polyol 6B. By performing the same synthesis operation, a product containing the hydroxyl group-containing monomer 6B was obtained.

[Manufacturing Example 7B]
Production Examples except that, instead of the polyol described in Production Example 1B, the polyol 6B shown in Table 1B was used and 3/4 equivalent of Calends MOI-EG (registered trademark) was reacted with the number of moles of OH of the polyol 6B. By performing the same synthesis operation as in 1B, a product containing the hydroxyl group-containing monomer 7B was obtained.

[Manufacturing Example 8B]
Production Examples except that, instead of the polyol described in Production Example 1B, the polyol 3B shown in Table 1B was used and 2/3 equivalent of Karenz MOI-EG (registered trademark) was reacted with respect to the number of moles of OH of the polyol 3B. By performing the same synthesis operation as in 1B, a product containing the hydroxyl group-containing monomer 8B was obtained.

[Manufacturing Example 9B]
Instead of the polyol described in Production Example 1B, the polyol 6B shown in Table 1B was used, and 1/2 equivalent of Calends MOI (registered trademark) was reacted with respect to the number of moles of OH of the polyol 6B. By performing the same synthesis operation, a product containing the hydroxyl group-containing monomer 9B was obtained.

[Example 1B]
10.33 g (5.5 parts by weight) of compound 1B obtained in Production Example 1B, 0.50 g (8.3 parts by weight) of Bis-GMA (bisphenol A diglycidyl methacrylate: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), E4BAD MA (Bisphenol A dimethacrylate ester 4 molethylene oxide modified compound SR540, manufactured by SARTOMER) 0.26 g (4.2 parts by weight), UDMA (2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate) 0.31 g (5.2 parts by weight), ETMPTA-3EO (Trimethylol propantriacrylate 3 molethylene oxide modified compound, manufactured by Kyoeisha Chemical Co., Ltd.) 0.37 g (6.2 parts by weight), MDP (10-methacryloyloxydecyl) Dihydrogen phosphate) 0.37 g (6.1 parts by weight), CQ (Camferquinone: manufactured by Wako Pure Chemical Industries, Ltd.) 6.1 mg (0.1 parts by weight), ethyl 4- (dimethylamino) benzoate (sum) Kojunyaku Kogyo Co., Ltd.) 0.018 g (0.3 parts by weight), BHT (dibutylhydroxytoluene: manufactured by Wako Junyaku Kogyo Co., Ltd.) 2.0 mg (0.03 parts by weight), 2-hydroxy-4-methoxy Benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) 0.015 g (0.25 parts by weight), barium aluminum borosilicate glass filler (GM27884, particle size 1.5 μm, 1.6% silane treated product, manufactured by NEC SCHOTT Components Co., Ltd.) ) 3.8 g (64 parts by weight) was placed in a container and stirred at 50 ° C. until uniform to obtain a composition to be used as a dental material. The composition of Example 1B is, for example, a composition suitable for evaluating the performance as a resin.

[Adhesive strength test method]
The bovine mandibular anterior teeth, which had been removed and stored frozen, were thawed under water injection, and root cutting and demyelination were performed. This was placed in a plastic cylindrical container having a diameter of 25 mm and a depth of 25 mm, and embedded in an acrylic resin. This surface was wet-polished with # 120 and # 400 emery paper, and the enamel and dentin planes were carved out so as to be parallel to the labial surface.
Next, compressed air was blown onto these planes for about 1 second to dry them, and then a plastic mold (manufactured by ULTRADENT) having a diameter of 2.38 mm was placed on the planes of enamel or dentin, and the prepared composition was prepared. After filling the mixture in batches, it was irradiated with a visible light irradiation device (Translux 2Wave, manufactured by Heraeus Kurzer) for 20 seconds to cure. Then, the mold was removed to prepare an adhesive sample. After storing the sample in warm water at 37 ° C for 24 hours, use a general-purpose testing machine (precision universal material testing machine 210X, manufactured by INTESCO Co., Ltd.), parallel to the enamel or dentin surface of the cow tooth, and in contact with the surface 1 A shear load was applied at a crosshead speed of 0.0 mm / min, and the shear adhesion strength was determined from the shear load when the composition formed in a columnar shape on the cow tooth surface was separated from the surface.
The results of the shear test of the obtained composition used as the dental material are shown in Table 2B.

[Comparative Example 1B]
A composition used as a dental material was obtained according to the operation of Example 1B, except that compound 1B was changed to HEMA (manufactured by Mitsubishi Rayon Co., Ltd., Acryester HO (registered trademark)). Further, the same operation as in Example 1B was performed, and the result of the shear test was obtained. The results are shown in Table 2B.

[Comparative Example 2B]
A composition used as a dental material was obtained according to the procedure of Example 1B except that compound 1B was not added. Further, the same operation as in Example 1B was performed, and the result of the shear test was obtained. The results are shown in Table 2B.

From the results in Table 2B, the hydroxyl group-containing polymerizable monomer for dental materials according to the second aspect of the present invention has improved adhesive strength with respect to cow teeth, especially enamel, as compared with conventional compounds for hydroxyl group-containing dental materials. It can be seen that it exerts a high primer action. That is, it was shown that by using the hydroxyl group-containing polymerizable monomer for dental materials of the second aspect of the present invention, it is possible to provide a dental material having a high priming ability to the dentin.

[Example 2B]
Compound 1B obtained in Production Example 1B 0.40 g (20 parts by weight), UDMA (2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate) 0.20 g (10 parts by weight), TEGDMA (Triethylene glycol dimethacrylate: NK ester 3G manufactured by Shin-Nakamura Chemical Industries, Ltd.) 0.20 g (10 parts by weight), MDP (10-methacryloyloxydecyldihydrogen phosphate) 0.26 g (13 parts by weight), CQ ( Kamferquinone: 0.020 g (1.0 part by weight), 4- (dimethylamino) 2-butoxyethyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.020 g (1.0 weight) Parts), ethanol (ultra-dehydrated: manufactured by Wako Pure Chemical Industries, Ltd.) 0.60 g (30 parts by weight), and distilled water 0.30 g (15 parts by weight) are placed in a container and stirred at 50 ° C. until uniform. A composition used as a dental material was obtained. The composition of Example 2B is, for example, a composition suitable for evaluating the performance as a bonding material.

[Adhesive strength test method]
The bovine mandibular anterior teeth, which had been removed and stored frozen, were thawed under water injection, and roots were cut and myelinated. This was placed in a plastic cylindrical container having a diameter of 25 mm and a depth of 25 mm, and embedded in an acrylic resin. This surface was wet-polished with # 120 and # 400 emery paper, and the enamel was carved out so as to be parallel to the lip surface.
Next, compressed air was blown onto this flat surface for about 1 second to dry, and then the composition prepared on the enamel flat surface was applied, and a weak blow of compressed air was blown to remove the solvent. This surface was irradiated with light for 20 seconds using a visible light irradiation device (Translux 2Wave, manufactured by Heraeus Kurzer). Further, a plastic mold (manufactured by ULTRADENT) having a diameter of 2.38 mm is installed on this, filled with a dental composite resin (manufactured by Venus Diamond, manufactured by Heraeus Kurzer), and irradiated with light for 20 seconds using a visible light irradiation device. And cured. Then, the mold was removed to prepare an adhesive sample. After storing the sample in warm water at 37 ° C for 24 hours, a general-purpose testing machine (precision universal material testing machine 210X, manufactured by INTESCO Co., Ltd.) was used to parallel the enamel of the cow tooth and contact the surface at 1.0 mm / min. The shearing bond strength was determined from the shearing load when the composition formed in a columnar shape on the cow tooth surface was separated from the surface by applying a shearing load at the crosshead speed of.
The results of the shear test of the composition for dental materials are shown in Table 3B.

[Examples 3B to 5B]
A composition to be used as a dental material was prepared by performing the same operation as in Example 2B except that the hydroxyl group-containing monomers 3B, 4B, or 6B obtained in the above production example were used instead of compound 1B. .. Then, the same test as in Example 2B was performed, and the result of the shear test was obtained. The results are shown in Table 3B.

[Comparative Example 3]
The same operation as in Example 2B was carried out except that HEMA (Acryester HO (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of Compound 1B to prepare a composition to be used as a dental material. .. Then, the same test as in Example 2B was performed, and the result of the shear test was obtained. The results are shown in Table 3B.

[Examples 6B to 13B]
A composition to be used as a dental material was prepared by performing the same operation as in Example 2B except that bovine dentin was used instead of bovine enamel and the compounds shown in Table 4B were used. Next, the same test as in Example 2B was performed, and the result of the shear test was obtained. The results are shown in Table 4B.

[Comparative Example 4B]
The same operation as in Example 6B was carried out except that HEMA (Acryester HO (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of Compound 1B to prepare a composition to be used as a dental material. .. Next, the same test as in Example 2 was performed, and the result of the shear test was obtained. The results are shown in Table 4B.

From the results of Tables 3B and 4B, the hydroxyl group-containing polymerizable monomer for dental materials of the present invention has higher adhesive strength with respect to cow tooth enamel and dentin as compared with the conventional compound for hydroxyl group-containing dental materials. It can be seen that it exerts a primer action. That is, it has been shown that the use of the polymerizable monomer for dental materials of the present invention has the potential to provide a dental material having a high priming ability on the dentin.

Claims (18)

A polyfunctional monomer for dental materials containing a compound represented by the following general formula (8A) in which the following core portion (X) and the following terminal group (Y2A) are bonded directly or via the following linking group (Z).

(In the above general formula (8A), n ^8aA indicates the number of terminal groups (Y2A) directly bonded to the ^{nuclear portion (X), and n 8bA} indicates the number of linking groups (Z) to the nuclear portion (X). ) Indicates the number of terminal groups (Y2A) ^attached, and the sum of n 8aA and n ^8bA is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y2A) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y2A) is at least one selected from the group consisting of the groups represented by the following general formulas (9a) to (9d) (meth) acryloyl group-containing group (Y3), (meth) acryloyl group, Alternatively, it is a hydrocarbon group having 1 to 20 carbon atoms, and the plurality of terminal groups (Y2A) may be the same or different, except that all the terminal groups (Y2A) in the compound represented by the general formula (8A) Of these, 3 or more are (meth) acryloyl group-containing groups (Y3) or (meth) acryloyl groups, and 1 or more are (meth) acryloyl group-containing groups (Y3).
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (8A), the linking group (Z) is used. Z) may be the same or different. )

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2A).) The polyfunctional monomer for dental materials according to claim 1, wherein the core portion (X) is a 3- to 12-valent organic group. The polyfunctional monomer for dental materials according to claim 1 or 2, wherein the core portion (X) is at least one selected from the group consisting of the groups represented by the following general formulas (6a) to (6j).

A raw material containing a compound represented by the following general formula (1A) in which the following core portion (X) and the following terminal group (Y1A) are bonded directly or via the following linking group (Z), and the following general formula (3). ) With the raw material containing the (meth) acryloyl group-containing isocyanate compound, (the number of isocyanate groups contained in the compound represented by the following general formula (3)) / (the compound represented by the following general formula (1A)). method for producing a dental material for a multi-functional monomer according to claim 1, in which an oxygen atom and the number of bound active proton and nitrogen atoms) = 1 ratio and reaction included.

(In the above general formula (1A), n ^1aA indicates the number of terminal groups (Y1A) directly bonded to the ^{nuclear portion (X), and n 1bA} indicates the number of terminal groups (Y1A) directly attached to the nuclear portion (X) via a linking group (Z). Indicates the number of bound terminal groups (Y1A), ^{the sum of n 1aA} and n ^1bA is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y1A) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y1A) is a (meth) acryloyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom, and a plurality of Y1A may be the same or different, except that the above general formula (Y1A) Of the terminal groups (Y1A) contained in the compound represented by 1A), 3 or more are hydrogen atoms or (meth) acryloyl groups, and 1 or more are hydrogen atoms.
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (1A), the linking group (Z) is used. Z) may be the same or different. )

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1A).)

(In the above general formula (3), R ^3a represents a hydrogen atom or a methyl group, and R ^3b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.) The method for producing a polyfunctional monomer for dental materials according to claim 4, wherein the terminal group (Y1A) is a hydrogen atom. According to claim 4 or 5, the (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is at least one selected from the group consisting of the compounds represented by the following general formulas (3a) to (3f). The method for producing a polyfunctional monomer for dental materials according to the above.

A monomer composition for dental materials containing the polyfunctional monomer for dental materials according to any one of claims 1 to 3. A dental material containing the polyfunctional monomer for dental materials according to any one of claims 1 to 3. A cured product obtained by curing the dental material according to claim 8. A hydroxyl group-containing monomer for dental materials containing a compound represented by the following general formula (8B) in which the following core portion (X) and the following terminal group (Y2B) are bonded directly or via the following linking group (Z).

(In the above general formula (8B), n ^8aB indicates the number of terminal groups (Y2B) directly bonded to the ^{nuclear portion (X), and n 8bB} indicates the number of linking groups (Z) to the nuclear portion (X). ) Is shown, ^{and the sum of n 8aB} and n ^8bB is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y2B) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y2B) is a (meth) acryloyl group-containing group (Y3) represented by the following general formula (9), a (meth) acryloyl group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom. Certain end groups (Y2B) may be the same or different, except that one or more of all end groups (Y2B) in the compound represented by the general formula (8B) are (meth) acryloyl group-containing groups (Y3). ) And 1 or more are hydrogen atoms,
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (8B), the linking group (Z) is used. Z) may be the same or different. )

(In the above general formula (9), R ^9a represents a hydrogen atom or a methyl group, and R ^9b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.)

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y2B).) The hydroxyl group-containing monomer for dental materials according to claim 10, wherein the core portion (X) is a 3- to 12-valent organic group. The hydroxyl group-containing monomer for dental materials according to claim 10 or 11, wherein the core portion (X) is at least one selected from the group consisting of the groups represented by the following general formulas (6a) to (6j).

The (meth) acryloyl group-containing group (Y3) is at least one selected from the group consisting of the groups represented by the following general formulas (9a) to (9f) according to any one of claims 10 to 12. The hydroxyl group-containing monomer for dental materials described.

A raw material containing a compound represented by the following general formula (1B) in which the following core portion (X) and the following terminal group (Y1B) are bonded directly or via the following linking group (Z), and the following general formula (3). ) With the raw material containing the (meth) acryloyl group-containing isocyanate compound represented by 1 / (the number of active protons bonded to the oxygen atom and nitrogen atom contained in the compound represented by the following general formula (1B)) ≤ (below) The ratio of (number of isocyanate groups contained in the compound represented by the general formula (3)) / (number of active protons bonded to oxygen atoms and nitrogen atoms contained in the compound represented by the following general formula (1B)) <1. The method for producing a hydroxyl group-containing monomer for dental materials according to any one of claims 10 to 13 .

(In the above general formula (1B), n ^1aB indicates the number of terminal groups (Y1B) directly bonded to the ^{nuclear portion (X), and n 1bB} indicates the number of terminal groups (Y1B) directly attached to the nuclear portion (X) via a linking group (Z). Indicates the number of bound terminal groups (Y1B), ^{the sum of n 1aB} and n ^1bB is equal to the valence of the nucleus (X).
The core (X) contains an oxygen atom or a nitrogen atom, and the atom bonded to the terminal group (Y1B) or the linking group (Z) is an oxygen atom or a nitrogen atom. It is an organic group
The terminal group (Y1B) is a (meth) acryloyl group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom, and a plurality of Y1Bs may be the same or different, except that the above general formula (Y1B) Two or more of the terminal groups (Y1B) contained in the compound represented by 1B) are hydrogen atoms.
The linking group (Z) is a divalent group represented by the following general formula (2), and when a plurality of linking groups (Z) are contained in the compound represented by the above general formula (1B), the linking group (Z) is used. Z) may be the same or different. )

(In the above general formula (2), n ^2a , n ^2b , n ^2c , and n ^2d indicate the number of units in each repeating unit, which are 0 to 100, respectively, and are n ^2a , n ^2b , n ^2c , and n. ^{The total of 2d} is 1 to 100, the left end of the group is bound to the nucleus (X), and the right end of the group is bound to the terminal group (Y1B).)

(In the above general formula (3), R ^3a represents a hydrogen atom or a methyl group, and R ^3b represents a linear alkylene group having 2 to 6 carbon atoms or a linear oxyalkylene group having 2 to 6 carbon atoms. The linear alkylene group or the hydrogen atom contained in the linear oxyalkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a (meth) acryloyloxymethylene group.) The method for producing a hydroxyl group-containing monomer for dental materials according to claim 14, wherein the terminal group (Y1B) is a hydrogen atom. The (meth) acryloyl group-containing isocyanate compound represented by the general formula (3) is at least one selected from the group consisting of the compounds represented by the following general formulas (3a) to (3f) according to claim 14 or 15. The method for producing a hydroxyl group-containing monomer for dental materials.

A monomer composition for dental materials containing the hydroxyl group-containing monomer for dental materials according to any one of claims 10 to 13. A dental material containing a hydroxyl group-containing monomer for a dental material according to any one of claims 10 to 13.